I

lN-l

600K

PV:nRT

- ,: #

A18

Idealgasequation,

22Ti has 22 electrons. The ion in TiOz is Tia*,

18 electrons. (ans)
which has (22 -

Since mass remains the same, n is constant'

4\:

P{t :

nTz

O St'p-bv-S&p

l04N

2.

Pl Q04l

nV
(27

PzVz

2pV

+273)
=

-!-

T2

or Iz:600 K

{ans)

The nuclear charge in neon is greater than

that in fluorine.

roNe

ls2

2s2

2p6

I sF

lsz

[93N P4 Q08l

2s2 2p5

Ne and F are both Period 2 elements. Across

the Period, ionisation energy (I.8.) increases
due to increasing nuclear charge and
decreasing atomic radii. Hence, the first I.E. of
Ne is higher than that of F. (ans)
O

tiY u *or'

CzHr(g) +

[+' .4

St+bv-sED

+C4H8G)

3.

c+

LH,
zcozb) + 2H2O(l)
3OzG) 4--"> ZCtJz(g

+3Qz(s)'

By Hess'Law,

LH":

mol of (Na2CO:)'.y(HzO2):0.100

:
molofCOz:

1.00

"
x

ffi

10-3

since Na2COt + 2H* -+ 2Na* + COz + H2O

(NazCOrLy(HzOz)

xNa2CO3 = x COz

mole ratio (NazCOr)".y(HzOz) : CO2: I : x

1.00 * l0-3 :2.00 x 10-3

:
:l:2

+ x=2
mol of KMnO4: 0.0500 ,<

kJ

mol-r (ans)
O

Sr+bv-sEp

mol

=2.0Ax l0-3mol

ffi

lt + lx : ry

[esN P3

Q0tl le0J Pr Q08l

MZ, JX, LY

L.E. cc .Q*Q- (r* + r-1

The ionic solid with the highest charge and
smallest size will have the most exothermic
lattice energy. (ans)

ffi$

:1.20 x l0-3 mol

),.y{}{zO z) = Y H2O 2
and 2KMnO4:5H2O2
since (Na2C

(NazCOr),.{HzO)

lHzOz= {Y

KMnOa

mol ratio (NazCO:),y(HzO): KMnOa : l:t!

: 1.00 l0-3 : 1.20 x 10-3

:l:I.2 "
+ 1y: 1.2 or y:3
.v 3 @ns)
Hence, ratio L:
i

D LG* : 1090 - 285 C7.3)

LG*:LH**fA,S*
: (2.A9 * 103) - (12 + 273)(44.1 - 51.4)
: -209A - 2SS (-:7 -3) J mol-r (ans)

llN-2
8.

NaC/O is formed.

When conc. aqueous sodium chloride (brine) is

electrolysed using carbon electrodes, C/z is
liberated at the anode and, H2 and NaOH are

order with
resnect to [NOrl

order with
resoect to [SO']

produced at the cathode.

Comparing expt2 and 3: [SO2] constant, when

tNorl increases by factor *ffi (ot 1.33 times),

Anode: 2Cl-(a$ -+ Cl2(g)+2{

relative rate increases by factor

Cathode: 2H2O + 2e- -+ 2OH- + H2

NaC/ + NaC/O +

Ie3J P4

9.

1.00

ft(0.006)(0.006)"
k(0.006x0.006)"
ft(0.005x0.005)"

(1.212:

(1.2)n*t=n:1

(ii)

o'

SeFbY-!!4

[SOz]' (ans)

Reaction is first order w.r.t. to

Qlsl

(ii)

copper

Cu
H,
Fe
Pb
Zn

+ 2e
Fe2* +
27g.*

2{
+2{

7712* +

Ze-

E*: +0.34 V
E*: 0.00 V
E*:4.44Y
E*:-{.13

E*:4.76V

Ndg) to be produced, hence rate

OSteFbY-S@

of

{ *tlme

The most suitable graph to plot is [C6H5N2+]

against l/time.

With respect to CoIIsNz* ion:

ifreaction is zero order, rate is constant
(i.e. vertical straight line graph);

if reaction is l"t order, rate cc [C6H5N2+]

Pt

Fe21aq) + Fe3*(aq)

To measure

[C6H5N2+] against l/time

Since the rate of reaction is followed by

measuring the time taken for a fixed volume

To remain in the reduced state, the metal must

have E* value more positive than that of
2H*lHz. Hence, copper will not be dissolved
by tap water containing carbon dioxide. (ans)

:
t.44 :

From expt.2, 1.44

a SteP-bY-ssP

6u2+ + 2e-

p62*

Let rate equation be: rate: frlNOz] [SOz]'

Fromexpt. l, 1.00 : ft(0.005)(0.005)" (i)

H2O (ans)
O

(or l.3f

times). .'. Reaction is frst order w.r.t. [NOz].

The overall reaction is:

2NaC/ + zHzO + 2NaOH +Ht+ CI2
As the solution is continually stirred, the
products of electrolysis are allowed to react.
Hence sodium chlorate(I), NaC/O, is formed.
C/z + 2NaOH

ffi

E*

(i.e. straight line graph through origin);

if reaction

2nd

order, rate

[C6H5N2*]2

(i.e. parabolic curve). (ans)

for the reaction

Fe3*(aq)* e-

is

e SkFby-St@

Fe2*(aq)

the right-hand half-cell consists of Pt electrode

immeised in a solution containing Fe2*(aq) +

Fe3*(aq) at 1.0 mol dm-3 concentration. (ans)
@

Stqbv-SeP

The pH of a buffer solution increases very

slightly when small amounts of base are
added.

A buffer solution is one whose pH remains

almost unchanged (i.e. only very slight change
in pH values) on dilution or when small
amounts of acid or base are added to it. (onsl
'' i'---

_\:

The element

*'ith the highest electrical

conductivitf is aluminium.
A/ has 3 valence electrons available to carry
the current {s'hile \a has I valence electron,
Mg has 2 r'alence electrons) and so, has the
highest electrical conductivity. (ans)
fsu{fur i-s S. i"niiephosphorus ls Pr; Si @iant
covalentt a.rt 4rgrlest meltingpoint;P'- is the
talg;.r; J7r:t-Jn .'-hile C/- r.s the smallest anion.]
O

Strbv-SEp

[03J

The H-I bond is weaker than the

bond.

1N-3

Pl Q23l

H{l
number of
moles of
oxygen gas

Iodine is a larger atom than C/. Hence, H-I

bond is loneer and weaker and so, is easily
broken. Thus HI decomposes into its elements
when heated but HC/ is stable to heat. (ans)
@

Step-bv-Sl@

no. of C atoms in alkane

Alkanes have general formula C,Hz*2.

600 cm3

C,IIz*z + (n

Ca(NOr)z(s) -+ CaO(s) + 2NOzG) + YzOz(E)

mol of 02

: \ x mol of Ca(NO:)z
I ..82 :0.0250mo1
--Tn-tu

Since molar gas volume

:24

+ zP)O, -+ nCOz + ff

.'. mol of 02: n +ry : t+u = trn**

.'. plot of mol of Oz (I) against no. of C atoms
(n) is a straight line gaph, with gradient= tr
and

dm3 at r.t.p.

f-intercept:

+.

(azs)
o sl*bv-Sts

vol of Oz = 0.0250 x24 x 103:600 cm3 (ans\

O SleFbv-Step

21.

C
C

CH2:CHC/ is unreactive as the C{/bond is

strengthened by the overlapping of theporbital of C/ with the a orbitals of C:C bond.
Hence, the C-C/ bond is too strong to be
broken. (ans)

In alkaline solution, HzOz oxidises Cr3*; itself

being reduced to H2O. Hence O2@) is
produced only under acid oxidation. (ans)
O SErbY-Sr@

o srbY-Stee

22.

B
W

AI

Si

Among the Period 3 elements, Si has the

highest melting point and hence, the highest
enthalpy change of fusion (due to its giant
covalent structure; a lot of energy is required to
overcome the strong covalent bonds between
Si atoms before melting occurs). Xis Si. (azs)
eFby-Step

The terminal carbon atoms

(l

and 4) are

sp2 hybridised.

Cl

and C4 aregpl (and not sp2) hybridised and

so, has a tetrahedral geometry while C2 and C3
are sp hybridised. The molecule decolourises
warm acidified KMnO+ as the primary alcohol

group at

Cl

is oxidised to

The electrons on the C/ atom delocalise

into the trbond.

only the acid oxidation

In acid solution, Cr2O72- ions oxidise HzOz to

Oz$);itself being reduced to Cr3*.
Cr2o12- + 3HzOz+ 8H+ -+ 2Cf* + 3Oz+ THzo

H2O

{O2H.

(ans)
O

Stelbv-Sto

@i",

Spl substitution is a two-step process that

involves the formation of a carbocation
intermediate (via heterolytic fission of C-X
bond). (ans)
23.

B @.t

zcozl

"o$ot

With steam/H*, acid hydrolysis of ester occurs

together with addition of H2O across C:C
bond.
Don.,'

@."rcoro
I steam, H*

@.n

zcoz'

* Ho$ou

@ns)
e Sl+i-.'-SE

lN-4
To give CHI: with alkaline aqueous 12, the
compound must have either CH3CH(OHF
group (compounds P and Q) or CHrCO- group
(compound R). (ans)

24.

fastest -+
z
w

slowest

OStctlr:lep

Ease of hydrolysis: RCOC/ > RC/ >

ArCi.

Acid chloride (W) is most readily hydrolysed

because the C atom carries a considerably
larger positive charge since it is attached to two
strongly electronegative atoms (O and C/).

27.

9o-.

NH

A (QF/"
-/

Chlorobenzene (X) is least readily hydrolysed

because the aryl-C/ bond is strengthened by
the overlapping of the p-orbital of Cl with the
aorbitals of the benzene ring.

.CozH

Jcoct

@;',''

PC/5

CH2OH

(CH3)3CI (Z) is hydrolysed more readily than

(CH3)3CBr (Y) because C-I bond is longer and
weaker than C-Br bond and so, breaks more
easily. Hence, rate of hydrolysis is in the

wann

I rvn
I h.ut

order: W (fastest) > Z>Y > X (slowest). (uns)

Fby-S&p

.o",

@|cH,rur,
llnternal condens ation
reaction

to

form cYclic

amide,Yj

c 6,, +'2@q)#d.*,

,o.r

NH

-/
(*1"'1ons1
O Step-bv-Stil

CI

For benzene ring to undergo electrophilic

substitution,Cl2cannot be in the aqueous state.
In the presence of water, A/C&(s) is rapidly
hydrolysed and would no longer be able to

function as a halogen-carrier. (ans)

28.

X
D

cHo

cH2oH

co2H

co2H

CO"H
I

c02H

O Stry-!Y:S!9P

has 2 chiral
centres

reacts with alkaline aqueous

iodine to sive tri-iodomethane

P only

P,QandR

X, Y and Z all react with Na to release H2(g)

suggests the presence of -OH group' Only one
of them reacts with 2,4-dinitrophenylhy drazine
(2,4-DNPH) suggests that only one of them is a
carbonyl compound. Hence, option D. (ans)
O

St+by-Skp

HH

",.-+-+-cH,
OH OH

(C+HroOz)
has 2 chiral centres

marked by *.

I
H

",.-fi-+-cH:
ooH

n,.-fr-fi-cH,

oo

Q (C4H8O2)
- has I chiral centre
marked by *.

R (C4H6O2)
- has no chiral centres.

(+)

- NH.

B oo.c*co?
I

In glutamic acid- the pK" values of 2.1,4.1 and

9.5 correspond to the a-carboxylic acid, the
side-chain carboxllic acid and the a-amino
group respectivell'. Hence atpH 7, basic -NH2
is protonated to form positively charged -NH3*
s-hile acidic {O:H grouPs are deprotonated to
(cns)
forro negtivell' cbarged {Ot.
O SEP-bY-steP

l1N-5

(t

./2

H3N

X and Zhave the same empirical formula'

X and Y are isomers.
The M, of Y is exactlY twice that of Z.

.1 3

H:N

X
Y
Z

alkene

,,ester

:coicrr,cH,
...--;.,'

CoHsNO

CrzHrNzOz

C6H5NO

CeHsNO

CTHsNO

X and Y have the same molecular formula and

so, are isomers.
Since Y contains twice as many number of
each atoms asZ,the M of Y is exactly twice
(ans)
that of

reaction). (ans)

Z.

It is the sum of the relative atomic masses

of all the atoms within the molecule.

Relative molecular mass, Mr, of a substance is

defined as the ratio of the avorage mass of one
the mass of an
molecule of the substance to
l2C

For a zero order reaction, the rate equation ts

rate: fr[P]0 or tate: fr; i.e- rate is constant'
Hence when rate is plotted against time, a
horizontal straight line graph is obtained.

l2C

isotope, expressed on the

scale. It is given by the sum of the relative
atomic masses, A,, of all the atoms within the
atom

of

molecule. (ans)
o s!eE!n!@

./ I
( 2

the use of hydrogen gas at 101 kPa

Since rate constant /c is a constant value, plot of

rate constant against time is also a horizontal

straight line graPh.

32. [11N Pl Q32 Electrochemical Cellsl

C12H16N2O2

empirical formula.

When oseltamivir is heated with HC(aq), acid

hydrolysis of both the amide and ester groups
occur and the basic amino group is protonated

empirical
formula

Hence all three compounds have the same

oseltamivtr

(acid/base

molecular
formula

(l atm)

measurement of the e.m.f- when the

current delivered by the cell is effectively
zero,

The standardhydrogen electrode consists ofa

platinised platinum electrode immersed in a

iolution of t.Oo mol dm-3 If ions. H2 gas at a

pressure of I atm (101 kPa) is bubbled over the
Pt electrode.
The extemal circuit that connects the two halfcells has a high resistance volftneter which
prevents the passage ofcurrent; i-e. current
delivered by the cell is effectively zero.
Since concentration ofsolution at hydrogen
electrode is 1.00 mol dm-3, pH : -logro(1.00)
or pH = 0. (ans\

k:

Ae-EnRr,the
From Arrhenius equation:
value of rate constant k increases with

,a-o"ru*."

t ,or",

.r*_r_.,lesJ P4 Q3sl

35.

Aluminium ions have

charge/surface area ratio.

The H-O bonds are weaker in

a large

[A(H2O)613* than in HzO'

A solution of AlCh is acidi'C due to the

relatively small but highly charged A/3* ions
which polarises the surrounding H2O
molecules, thereby weakening the O-H bonds
in tA(HzO)u13* and causing them to gle up H*
ions.

A/Cir(s) + aq -+ [A(H2O)6]3*(aq) + 3c/*(aq)

+
[A(H2O)613* -+ [A(H2O)5(OH)]2* H* lazs)

llN-6
39.

36.

./ t

./ 2

1
2
3

Br:
SOz

HBr is formed by the reaction ofNaBr with

Tollens'test

A dilute alkaline solution of KMnOa loses its

conc. HzSO+.

NaBr+ HzSOr

pink colour in a positive Baeyer's test suggests

that oxidation number of Mn is reduced from
+7 (in KMnO4) to +4 (in MnOz).

HBr+ NaHSO+

The HBr produced reacts with propan-l-ol to

give l-bromopropane. However, some HBr is
oxidised by conc. HzSO+ to Brz.

A silver mirror formed in a positive Tollens'

test suggests that oxidation number of Ag is

2HBr + HzSOa + Br2 + SOz + 2H2O

reduced from

+l (in Ag(NIH3)r*)

to 0 (in Ag).

A red precipitate of CuzO formed in a positive

Fehling'test suggests that oxidation number of
Cu is riduced from +2 (incomplexed Cu2*; to
+1 (in CuzO). (ans)

By-products are Br2 and SOz. @ns)

,/ I

Baeyeds test
Fehling's test

SicElYr$lA

O St@-W-St@

It contains

an amide group.

40.

I
2
(cH3cH

van der Waals' forces

hydrogenbonding

The type of bonding that occur in the tertiary

structure are R group interactions.
l..ut

The R group in alanine

({Hr)

and in glycine

(-H) can only form van der Waals'forces.

The R group in serine

({H2OH)

can form

hydrogen bonding. (cns)

Tamiflu@

O Sbp-by-St.p

Hence, the Tamiflu@ molecule contains one

amide group and one amine group. It has only
one (and not two) ester group and, three (not
(ans)
four) chiral centres marked by

*.

PI MCQ KeYl

Key

2D
3C
4D
5C

38.

[11N

zCO + 2NO -+ 2CO2 + N2

In a catalytic converter, the three main

pollutants (CO, NO, and unburnt

6C
7D
8C

hydrocarbons) are converted into the less

harmful CO2, N2 and water vapour.
CO (or unburnt hydrocarbons) reduces the
oxides of nitrogen to N2.
NO, oxidises unburnt hydrocarbons to COz and
HzO; itself being reduced to N2.
CO is oxidised to COz. @ns)
Q

slctrly-sEp

9A

10D

O.

Ker

1l c
T2B

O.

2lc

Kev

t4B

228
23B
24B
25C

L7C

26A
274
28D

138

15c
t6c
18A
19C
208

298

30B

O.

Kev

3tD
32B
33A
348
35C

368
37D
38D
394
408

1lN-7

4.
1.

Turn offthe heat and carefully add2 -3 cm3

of water down the vertical condenser to the hot
reaction mixture (to hydrolyse any unreacted
ethanoic anhYdride).

(a)

(i) (cHrco)zo + HocoHacozH

-+ CH:COzC6I{4CO2H + CH:COzH (ans)

5.

When the reaction has subsided, carefully pour

the flask contents into 50 cm3 of cold water in
a small (100 cm3) beaker placed in an ice-bath'

(ii) M, of (cH:coho

6.

Allow the beaker contents to cool, scratching

the inside of the beaker with a glass rod if
crystallisation does not occur immediately'

: \t:u,

+ 6(1.0) + 3(16.0)

M, of HOC1H+COzH = 7 (12.0) + 6(1.0) + 3(l 6.0)

Stand the beaker and contents in the ice-bath

until crystallisation appears to be complete'

138

M, of aspirin = 9(12.0)+8(1.0)+4(16.0)

7.

:180

l0 g aspirin,
x
of (CH3CO)2O: s} 102:5.67 g

From equation in (i), to prepare

mass

Since typical yield of aspirin is75o/o,

mass of (CH:CO)zO

Similarly,
mass of HOC6FI4CO2H:

(b)

8.

ry
:7.56 g (ans)

used: 5.67 "

# t
10.22

138 *

g.

(ans)

Assembled apparatus to heat reaction mixture:

(c)
water out

o
water in

-+

beaker

Filter the solid product (aspirin) using vacuum

filtration (Buchner funnel) and wash the solid
with a little cold water (to remove CHTCOzH
and HrPO+ which are water-soluble).
Recrystallise the solid product (aspirin) using a
minimum of hot water, filtering and washing
as before (step 7). Putl airthrough the aspirin
crystals to remove excess moisture. Dry the
aspirin crystals in air'
Determine the melting point of the dry aspirin
crystals to check its purity. If the sample is
oC- (ars)
pure, it should melt sharply at 135
Ethanoic anhydride is corrosive (can cause
burns) and its vapour is initating to the
respiratory system.
To minimise this rislq carry out the experiment
in a fume cupboard and avoid direct contact
with skin or inhalation of vapour. Wear
gloves and safety goggles when handling this

chemical. (czs)

oil bath
boiling chips

t
heat
heat

2.

3.

&: ffi

(b)

[PCl4]* is tetrahedral in shape, while [PC/6]- is

@ns)

Procedure:

l.

(a)

Weigh out as accurately as possible 10-2 g of

2-hydroxybenzenecarboxylic acid and add it
into a round-bottomed'Quickfit' flask-

Carefully add 7 cm3 of ethanoic anhydride

using a l0 cmr measuring cylinder (in a fume
cupboard). Then carefully add 8 - 10 drops of
85 % phosphoric acid and swirl the flask
gently to mix the contents.
[vol of (CH3CO)2O: ;ffi: ;ft:7 cm3]
Add some boiling chips and place a condenser
on the flask as shown above. Heat the mixture
under reflux in an oil bath for about 15 mins.

moldm-3 (ans)

mshaPe

[rFj

@ns,

lN-8
4.

3.

(a)

PC/5G)

1.00
equilmimol (l-x)

PC/i(s)+ClzG)

0
x

initial/mol

0
.r

PC/r + 4H2O -+ 5HC/ + HrPOa

5(l-x) (l-x)

(l-x)

(a)

(i) Group II elements conducts electricity in the

solid state (due to presence of mobile
electrons) and hence, are metals. (ans)
at room conditions, C/2 is a gas,
Brz is a liquid while 12 is a solid.

(ii) chanqe:

mol

HCI: [f and HfO+ :2*

mol of Ff formed :5(l-r) +2(l*x)
Since

:7(l-x)

explanation: Down the group, as the halogens

increase in size, the number of electrons
increases and so, the strength of intermolecular
van der Waals' forces of attraction increases.
This leads to an increase in boiling point and
hence, a decrease in volatility of the halogens
from chlorine to iodine. (ans\

mol

PC/, + 3HzO -+ 3HC/+ HrPOr

x mol

3-r

mol r mol

Since HC/ = H* and H3PO3 = 2H*

mol of H* formed :3x * 2x: 5-r mol
total mol of H* formed :7(1-x) + 5x
= (7

*2x) mol (ans)

(b)

(i) mol of H* in 25.0 cm3: mol of NaOH reacted

tf

in 1.00 dm3:

#'o.tag0

ffi
:

(c)
(ans'1

(7 -2x)

-x
: I - 0.508 :0.492 mol (ans)
mol of PC/-. =.t: 0.508 mol (ans)
mol of C/: : r: 0-508 mol (ans)

mol of PC/s = I

(i)

+# :

[PC/:]: [C/:]:

Si-C/:

!. :
r\'

Pc/5]

mol-1 (ans)

359 kJ

mol-r (ans)

atom does not have d-orbitals and so, cannot

form co-ordinate bonds with water molecules.
However, Si atom in SiCL has available lowtying empty d-orbitals, which can accept lone
pair of electrons from water molecules and so,
allows dative (or co-ordinate) bond formation
between HzO and Si before the Si-C/ bond
needs to be

:0.1016 mol dm-3

[PCi3][C/r]

340 kJ

(iiD CC/4 has no reaction with water because C

0-0984 mol dm-3

+#

sic/4 + Z}jzo -+ Sio2 + 4HCI (ans)

(ii) C{/:

rcl Since volume of original flask:5.00 dml

PC/.1 =

from carbon to

energy to overcome. Hence, the melting points

decreases from carbon to germanium- (ans)

(ii) From (a), mol of H* in l Oo dm3

(7 - 2x): 5.984 =+ .x : 0.508

(ii) As the atomic size increases

= 0.1496 mol

:5.984 mol

Solid carbon, silicon and germanium have

giant covalent structures. (ans)

germaniumo the covalent bond between atoms

becomes longer and weaker which requires less

:4.00 x

(i)

ffi

:4.00 x
mol of

(b)

broken. (ans)

(d)

(i)
mass / q

(0.1016x0.1016)

no.

of

mole

:0.1049 mol dm-3

:0.105 mol dm-3 (ans)

CI

46.7

1.76

N
6.t4

46.7

1.76

6.14

35.5

l-0

14.0

1.32

simplest t.32
65Tdratio

z,

l-76

Pb
45.4
45.4
207

a.$9 :4.2t9

L 0.439 .-,
-!-J3-=
61i9- o.219

0.219
0 219

empirical formula of Y is C/oHeNzPb. (ans)

(ii)

anion: [PbCt6]2- cation: NHa* @ns)

(iii) oxidation state of Pb in Y : +4 (ans)

(iv) Lead-containing ion: octahedral shape. (azs)

i"l

E*lv
+1.69

Pb* + 2e -+ Pb2*
y3* + H2O -+ VO2* + 2ff + e

-o.34

ffF

lN-9

HrO+pb2*+2VO2*+4If
E*""il: (+1.69 - 0.34) V : +1.35 V

6.

Since

(i) White solid formed is silver chloride. (ans\

*""n > 0, the reaction is feasible'

pt*

pb# + Zt

+1.69

->
vo2*+Hzo+vor*+2rf

*.

ffiTrH2O+pb2*
Euun=(+1.69

Sin;E*""1>

-1S
--+4If
+2VOi

v:

+0-69 V
1.00)
0, the reaction is feasible'

(a)

(ii) Chloroalkane (or halogenoalkane) functional

group is present in W; i.e. 1H?Cl. (azs)

(iii)

phenol and alcohol groups. (ans)

(iv) Reaction 5 confirms

presence of phe4Al group'

Colourless solution formed with NaOH(aq) at

r.t. suggests that W is acidic enough to react
with NaOH (hence, not alcohol). (ans)

In acid solution, PbC/a oxidises V3* to VOt*,

andthento VO1+ @ns)
5.

(a)

(i) Functional group is alkene (C:C).

K decolourises Br2(aq) suggests the presence
ofC:C bond. K has only one C:C bond
because molecular formula of K shows that the

3, W undergoes oxid4tion' Since

W has a phenol gtoup, deduced from the
molecular formula of W (CrHzOC/) that the
other side chain in W is -CHuCl, which is

(b) In reaction

oxidised to -COzH.
:
Molecular forrnula of organic product CzHoOr
:
check: M, : 7(t2.0) + 6(1.0) + 3(16.0) 138
(ans)

carbon chain has general formula CnHzn (which

is that for alkene with one C:C bond). (ans)

(ii) Functional group is alcohol (-OH).

K reacts with excess Na(s) to give H2@)
suggests the presence of -OH group.
R-OH + Na -+ R-O- Na* * trH,
since molar gas volume

mol of H2 formed : #
Since 0.10 mol of

:24

(c)

(i) ln reaction 2, the phenol group reacts to give

the corresponding tribromophenol-

:142.5 and M of white

:379.2,
solid product formed
:236'7
difference in M,= 379.2 - 142.5
Since M. of CzHuOCl

dm3 atr.t.p.,

:0.10 mol

approx. no. of Br atoms in product

K gives 0.10 mol of H2, and

(b) Possible stereoisomers of K:

o

shows optical
as the molecule has no plane of
isomerism "(oH)cH2oH
*) and the
symmetry (chiral C marked by

CHr=6gf

"i

)c-o-n

.H'l

"'/"\o-t

*,-c\"-H

(iii)

-H
(iv)

CH2(OH)CH:CHCH2OH shows cislrans

isomerism due to restricted rotation about C:C
bond and each C atom ofC:C bond has two
different groups attached to it.

Hs

H4i/

)E*"

). :"a,,

H/

crs- lsomer

{Y
-c-o-H

H
\.:.'

rd

Presence of p!94q1group

confirmed. (ans)

(v) Reaction 3. The oxidation product is a benzoic

acid which suggests that W is an alkylbenzene
(i.e. aromatic). (ans)
(d)

(i)

\ilis qi-"
H

H-O

(ans)

(ii)

In reaction 2, a tribromophenol is formed

suggesting thatC-2 and C-4 with respect to
phenol group must be free.
Hence, W is di-substituted at C-1 and C-3.

In reaction 1, white solid of AgC/ fonned

\H
A H ,rorr- (ans)

The white solid is forrned by substitution, and

not by addition, confirms that W is an aromatic

compound. Alkenes are the only aliphatic
compound that reacts with Br2(aq), in which
case electrophilic addition occurs. (ans)

/H

"-ol\'"
H--?Zc-H

:3

(iD Electrophilic substitution takes place' (ans)

images formed are non-superimposable-

mirror
H.

?f!t

Molecular formula of white solid: CzlI+OC/Brr

check: M, : 7 (12.0)+4( I .0)+ 1 6.0+3 5' 5+3 (79'9)
:379.2 (ans)

-OH gives Imol of Hz,

I molecule of K has two alcohol groups. (ans)

each mol of

suggests that W undergoes hydrolysis and son

Cl atomis not attached directly to the benzene

ring. Hence, C/ atom is in the aliphatic sidechain; i.e. --CH2CI side-chain. (ans)

tlN-10

M-N=C:O is hydrolysed to give a

primary amine and COz, which reacts with
OH- to give a carbonate. If NaOH(aq) is used
in stage fV, then the other product is Na2CO3.

(iv) In stage

l.
(a) Let oxidation number of iodine be x.

R-N:C:O+ 2OH- -+ R-NH2 + CQ32- (ans\

4(*1):-l = x: *3
oxidation number of I in lC[ = a3 (ans)

1g

(e)

step

rcl;

c/F5

r'3

i .'i3
:;'.
;i x^rx i.
3

p..'YJ'..it3

Br2; anhydrous A/C/: (as halogen-

carrier) (ans)

(b)'Dot-and-cross' diagrams:

V:

[:i1.

" .irl-

acidified KMnOa; heat (ans)

step

VII:

PC/5i room temperature (ans)

e from cation)

C/Fs has 5 bondpairs and I

lone pair of electrons around
the central C/ atom and so,
is square pyramidal in shape.

VI:

step VIII:NH3;

[''ir:l:TJ
(A denotes

step

roofi temperature (ans)

"6H

is ?oNH,

Br

Br

@ns)
o ste}by-SEp

.)*{'
2.

IC/c

has 4 bond pairs and 2

(a)

lone pairs of electrons

around the central I atom
and so, is square planar
in shape. (ons')

(i) mass of gas evolved

L,r-&1

pV:nRT

(i) HC/O + If + 2{

ff

(ii) mol of Iz

(ii)

: ** 0.0050 *t&:1.50'10-smol
mol ofN-chlorosuccinimide

33.5

@ns)

(ii)

lo

R{:

+HBr
+Brz+R-C. /o
(ans)
\u,
'NHB,

Oxidation state of Br in

A: *l

two lone pairs of electrons.

atom:

RT

1.00x105x193x10{
8.31x 298

(ans)

mass of other gas

:0.562 - A3$ :0.219 E

M.of othergas:

!RT
pV
0.219x8.31x 298
1.00x105

(ans'1

(iii) N atom in compound B has one bond pair

no. ofelectrons aroundN

pY

M, of COz : 12.0 + 2( I 6.0) : 44.0

mass of COz:0.AO779 x 44.0:0.343

(d)

(i)

193 cm3

:0.00779 mol

1.50 xl0-5 x133.5

:2.0A *10-3

r: #)

vol of other gas : 386 - 193 : 193 cm3

mol of COz : mol of other gas

mass of N-chlorosuccinimide

(since

The gas is carbon dioxide, which is acidic and

so, reacts with NaOH(aq) in an acid-base

M, of N-chlorosuccinimide, Cy'IaNO2C/

0.438

reaction. (ans)

mol of Iz
1.50 x l0-5 mol

= 4(12.0)+4(1.0)+14.0+2(l 6.0)+35.5

=#*,

(iii) vol of COz(g) =

Since N-chlorosuccinimide = HC/O = Iz

t,r- ffi o"- 0.562x8.31x298

r,t
pV"' 1.00x105x386xl0-6
:36.1 (ans)

-+ C/- + HzO
2T -+ lz+2e+ 21, -+ Cl- +lz+ H2O (ans)

: * t mol of SzOr2-

1.00

:0.562 E

Using ideal gas equation,

(c)

HC/O +

xl93xl0-6

: 28.1 (ans)
the other gas is carbon monoxide. (ans)

and

(iv)

Salt E is CaCzO+. (ans\

CaC:O+(s)

CaO(s) + COz(g) +

CO(g) (ans)

lN-l I

(b)

it]::l
(i) In malonic acid' the first acid proton
uother" -{O2H group stabilises
r""Jify

"*,ft"
p
HOzCCH2COt
anion formed bY
fl, p;
intramolecular 01
i'a-intramolecalar
ttnatoe"n bonAing o-H
iffi*ffirfis so much less lrydrosen
bondine
malonic acid

the

-)

pK1

vol of NaOH in excess: l0 cm3

mol of NaOH : 0.10 x #: 1.0 x l0-3 mol
total vol of mixture = 10 + 30:40 cm3
x 1.0 x l0-3
=

INaOH]

is very

(iv)

[OHl

:#

:0.0250 mol

pOH

[rr]:@

: -logto [OHl
: -leg16(0.0250; :

1.60

(c)

(i) F is O:C:C:C:O; linear in shaPe' (azs)

(ans)

t2.40

pH
5.70

(ii)

Product formed:

with NHIG)

o\f /o
/t f,-tt*",

with HC(g)

(ans)

dil. NaOH(aq)

(d) BCH2CH2BT +

vol. of NaOH /

When vol of

NaOH:0

cm3,

PH:

ln*t-

1.92

(only l0 cm3 of malonic acid present).

HOzC-COzH

At frst end-point,
HOzCCHzCO2H + NaOH

BTCH"CHTBT

ethanolic KCN
heat

-+ HO2CCHzCOz 53+ + H2O

[NaOH],
acid: 10 cm3
malonic
vol
of
vol of NaOH:

At point of half-neutralisation of
HO;CCH2COzH, vol of NaoH: 5 cm3
since [HO2CCH2CO2H]
so, pH p/,t:2.85

[HO2CCHzCOz- Na*]

(point of maximum buffer capacity)

NCCH2CH2CN
I dit rte

I ursoo(aq),

since [HO2CCH2CO2H]

HOCH2CH20H

lK"cr,o"Af

(ans)

cm3

o\T lo

,,/ I;'-.,

",^
0510ls2030

dm-3

pH :14-pOH
: 14 - 1.6: 12.40 (ans)

Jt.+txto-3xo.1o

:0.01l9 mol dm-3

pH:-logye[H*]
= -logro (0.01197 : 1.9,

[-O2CCHzCOz-]

When vol of NaOH = 30 cm3,

ff

small, [Ho2ccH2co2H]eqm = [Ho2ccH2co2H]6

(another point of maximum buffer capacrty)

:+ Kr : 10-2'85 :
Since

10:20crr.3

since [HO2CCH2COI ]
so, pH = PKz: 5.74

-logro Kt:2.85

l.4lx10-i mol dm-3

the degree of dissociation, a,

Na* + 2H2o

At point of half-neutralisation of
gOrCCffrCOi, vol of NaOH: 15 cm3

acid proton is held more tightly by the monoanion via intramolecular hydrogen bonding and
so, it is difficult for malonic acid to lose its

(iii)

-o2ccH2cof

=2x

(ii) Th" pf, value of malonic acid is higher than

th. p& of ethanoic acid because the second

second acid proton. In addition, it is

electrostatically unfavourable to remove a
from the negatively charged anion. (ans)

Na*

since [HOzCCH2CO2H] = [NaOH],

vol ofNaOH = 2 x vol of malonic acid

acid' (ansl

than the pK1 of ethanoic

At second end-Point,
HOzCCHzCO2H + 2NaOH

tI heat

HOzC-CHzCHz{OzH
(ans\

llN-I2
(b)

3.

(i) Balancing P, gives

(a)

(i)

lon

c.*"

concentration / mol dm-'

_"r.it:

2.00x

:I
c:

l0a

#:2.02xlAa
cl- HP: 2.00x104

Mg*

0.0366 : 0.0366 : 6.00x

HCO3- 1.0+12.0+3(16.0)
61.0 !

Cl- : HCOr2.00"

l0{

: 6.00x

l0r

(ii)

I : I :

COdg) + H2O(l) + CO321aq)

(i) To prepare

10-6

- II
-rrt

When rainwater containing dissolved COz(g)

percolates through the rock, equilibrium I
shifts to the right as [CO2(g)] increases thereby
forming more HCO3-.

As a result, tcorlad] decreases which, in

turn, shifts position of equilibrium II and III to
the right thereby causing more CaCO:(s) and
MgCO3(s) to dissolve. Hence the resultant
solution (mineral water) contains Ca2*, Mg2' ,
C/- and HCO3-. @ns)

mol dm-3 (ans)

PC/3, dry Ci2 is passed over heated

Pa (which is in excess).

white phosphorus,

Pa+ 6Clz--> 4PClz

To prepare PCl5, an excess of dry C/2 is passed

over heated white phosphorus, Pa.

P4+ l0cl2-+ 4PCl5 @ns)

-I

The rock is probably composed of mainly

CaCO3 and MgCO3 (and some CaC/z and
MgCl) which dissolve sparingly in water.

CaClz(s)
Ca2*(aq) + 2Ct-(aq)
==
MgC/2(s) + Mg2*(aq) + 2Cl-(aq)
CaCO:(s)
Ca2*(aq) + COrlad
=
MgCO3(s)
Mgz*(aq) + CO:21aq)

3x= 3 x 2.47

mol dm*3

(c)

3(ans)

2HCO31aq)

10-6

2.417

= i.42 * l0{

Since Group II salts become more insoluble

down the group, &o (CaCOr) < K,o (MgCO:)
and so, ionic product [M'z.][CO3t-1wiU exceed
K.p (CaCOr) first. Hence CaCOr(s) is the first
solid to be precipitated. (ans)

(iii)

[Ca'*]

Water is removed when the mineral water was

evaporated. This shifts the position of
equilibrium I to the left, forming more CO32-.

2x

= x: &/ro8: I,ft*to*yro8
x

l:3
4 :12

relative amounts of the salts are in the ratio

CaCI2: MgC/2 : Ca(HCO3)2 : Mg(HCO3)2

dm-rs (ans\

+ 2POa\aq)

=: 3Ca2*(aq)
3x
-r
:
&p [cu'*]'[Poot]'
: (3x)3(2x)2: 108x5

From the above table of ion concentrations.

: 2.00x 104 :2.o2xl0a

:l:l
:4:4

mol5

Ca:(PO+)z(s)

Ratio Caz* r Mgt*

[poo'-]'

1Ca2*13

(iii) Let solubility of Ca3(POa)2be x.

From the formulae of the salts,

Ratio Ca2*: Mg'*: C/-: HCO:-

:4:

SiF4 + 2HF + 3CaO + 9Ca3(PO4)2 @ns)

(ii) K,p:

Mg(HCO3)2. (ans)

:2

b:

6Cas@Or)f+SiOz+H2O

loa (ansl

Formulae of salts that could exist in the

solution are CaCl2,MgCl2, Ca(HCO:)z and

:2

/:9

Next balancing Ca, gives e: 3

Then balancing O, gives c
and
Then balancing Si, gives
I
and balancing F gives d: 2

(ii)

G is PoC/r.

@ns)

tetrahedral ^..-P.:. ct' \ c/

in shape. (t^)
POC/3 is

[check:

M= 31.0 + 16.0 + 3(35.5): 153.5]

(iii) By-product H is SO/e). (ans)

SO3 + PC/3

-+ POC4 + SOz

PC/5 + H2O

-+ POC/3 + 2HCl (ans)

(a) The secondarv stmcture of protein refers to the

detailed configurations of the polypeptide

chain, which may be coiled or folded or

puckered with the a- helix and the B-oleated
sheet being t$-o common repeating structural
patterns in proteins. Both structures are
stabilised by hydrogen bonds between the N-H
group of one amino acid unit and the C=O
goup of another along the main chain. (ans)

The tertiary structure of protein refers to the

overall 3-dimensional shape of the protein
involving folding or coiling of the chains. It
shows how protein molecules are arranged in
relation to each other. Fourtypes ofR group
interactions hold the tertiary structure in its
necessary shape - hydrophobic interactions
(van der Waals'forces), hydrogen bonding,
ionic bonding and disulfide linkages. (ans)

(ii) Fe2* ion in high spin state (H2O ligand):

The quatemary structure of protein refers to the

overall spatial arrangement of its individual
polypeptide chains (subunits). It shows how
the individually folded subunits are packed
together, and is stabilised mainly by
hydrophobic interactions between non-polar
areas on the surface ofthe subunits. (ans)

(b) Since the polypeptide chains spontaneously

coalesce into a haemoglobin molecule, the
overall process is spontaneous and so, AG is
negative. (ans)
Each step in the process (starting from the
formation of primary structure from constituent
amino acids to the secondary structure and then
to the tertiary structure and eventually to the
ouaternarv structure) involves bond formation
and so, AFl is negative. (ans)

lN-13

/1,
\+11]l
11

d-orbitals of Fe2*

d-orbitals of an
isolated Fe2* ion
Fe2* ion

in haemoglobin @ns)

in low spin state (O2ligand):

/1"
\1,

1r+l

d-orbitals of Fe2*
in haemoglobin @ns)

d-orbitals of an
isolated Fe2* ion

(iii)

Electrons usually prefer to occupy orbitals

singly, rather than in pairs, so as to minimise
repulsion between the negatively-charged

electrons. (ans)

(iv) Oxyhaemoglobin contains the larger energy

Eap,

E,between its d-orbitals because it takes

more energy to overcome the energy gap than

to overcome the repulsion between the
negative-charged electrons and so, Eillng of
electrons takes place instead of the orbitals
being occupied singly. {ans)

Once the quaternary structure is formed, there

is increase in orderliness and so, A,S is

negative. (ans\
(c)

(d)

(i) Electronic configuration of Fe2*: [Ar] 3d6

Fe2* has incompletely filled 3d-orbitals. In the
presence of ligands, the 3d orbitals become
non-degenerate and split into two groups with
slightly different energy (d-d* splitting). When

(i) A protein can be hydrolysed non-enzymatically

by heating (under reflux) with hydrochloric
acid (6 mol dm-3) for several hours. (ans)

a d-electron from the lower energy group is

promoted to the higher energy group (d-#

electron transition), radiation in the visible

region of the electromagnetic spectrum is
absorbed. The light energy not absorbed (in
this case, red) will be seen as the colour of
haemoglobin. (uns)

(ii) Piecing the fragments together:

met-asp-gly
asp-gly-ser
ser-ala-gly

gly-glu-ser
glu-ser-lys
ser-lys-tyr
amino acid sequence of the smallest
polypeptide is

met-asp-gly-ser-ala-gly-glu-ser-lys-tyr

(ans)
@-by-St@

lN-14

(iii) This is because 4-aminophenoxide ion, which

(a) Acidity: ethanol (

cH3cH2oH + H2O
H2O + H2O
c6H5oH + H2O

(b)

<

water

+
=
+

is negatively charged, is a betler nucleophile

than 4-aminoPhenol. (cns)

phenol

cH3cHzo- + H3o+ -I
OH- + H:O*
-II
c6H5o- + Hro*-IU

Ethanol is a !'eaker acid than water because

the negative charge in the ethoxide ion,
CH3CH2O-, is intensified by the electrondonating ethyl group, making it a stronger base
than the hydroxide ion, OH- (from water)'
Hence position of equilibrium I lies more tro
the left-hand side comPared to II.
Phenol is a stronser acid than ethanol (and
water) because the phenoxide ion, CoHsO-, is
stabilised by delocalisation of the negative
charge into the benzene ring. Hence position
of equilibrium III lies more to the right-hand
side compared to I (and II)- (ans)

(e) reaeent:

condition: roomtemPerature

(ans)

(ii)

Fe2*+Fe3*+e-

H2o+

orN@o-

+H3o+

e : mol of Fe2* : 5.65 x 10-3 mol

mol of e lost when Fe2* is oxidised
= 5.65 x10-3 mol ------- (l)

mol of

ln KC/O', oxidation no. of C/:2x-l

:
to reduce chlorine to C/- (oxidation no' -l),
each mol of KC/O' takes in 2x mol of e-'
:
M, of KCIO, : 39.I+ 35.5 * l6x 7 4'6 + l6x
given: mass of KC/O':0.150 g
molofKCiO,:7ffi: mol

condition: room temPerature (ans)

orN@oH+

mol of Fe2* :0'500 x ##

:5.65x10-3 mol

reagent: diluteHNO3(aq)

to the right-hand side'

(ans'S

(0
(i) 3Clr+ 6NaOH -+ 5NaC/+NaC/Or + 3H2O

To convert phenol to 4-nitrophenol:

(c) 4-nitrophenol is more acidic than phenol

because the electron-withdrawing -NOz group
stabilises the 4-nitrophenoxide ion formed and
so, keeps the position of equilibrium even more

aqueous C/2

:+

mol of

accepted when KC/O' is reduced

2x x mol of KC/O'

=(Lrxffi)mol ---'-(2)

Since mol of

e lost (l):

mol of e- gained (2)

5.65x10*3:bcxffi
x:

(ans)

(ans)

Half-equations for the reaction:

(d)

CtO; + 4H* +

(i) Reagents and conditions:

step

I:

Sn, excess conc.

HC/;

heat

(usually foltowed by adding NaOH to

free the amine from -NH3* salt)

II:

NaOH(aq); room temperature

step IV: CHICOC/; room temperature (ans)

step

(ii) Tvnes of reaction:

I:
step II:

step

III:

reduction
acid-base reaction (neutralisation)

nucleophilic (S12) substitution

step IV: condensation (nucleophilic
substitution) (ans)

step

4e-

Fe2*

-+ Cl- + 2H2O
-+

Fe3*

+ e(ans)