H2 N2007 Paper 2 Suggested Solutions

(a)

Alkane

(b)

C14H30 + 21.5 O2

14 CO2 + 15 H2O

OR
2 C14H30 + 43 O2

28 CO2 + 30 H2O

(c
i)

Mass of C14H30 burnt

= (10.8)(10700)
= 115560 kg or 116 tonnes

(cii)

Mass of carbon dioxide produced

= (44 x 14)/198 x 116
360 tonnes

(d)

Using PV = nRT
6 x 105 x 67.0 x 10-6 = n x 8.31 x293
n = 0.165 mol

(e)

As the volume of the tyre remains constants

PT

P1

T1

P2

T2

6 105
P2

293
278

P2 = 5.69 x 105 Pa or 5.69 bar

(f)

The difference between max. internal pressure and atmospheric pressure is

(8 1.01) bar = 6.99 bar.
The tyre will only explode if the difference between the internal and external
pressure exceeds this.
Difference between the internal pressure of the bicycle tyre at a height of
10000m and sea level = (5.96 0.28) bar = 5.68 bar
Therefore, its not necessary to deplete the tyre before flight.

(ai)

(cold)
2 NaOH (aq) + Cl2 (g)

(aii)

NaCl (aq) + NaClO (aq) + H2O (l)

(hot)

6 NaOH (aq) + Cl2 (g)

5 NaCl (aq) + NaClO3 (aq) + 3 H2O (l)

(bi)

NaCl (-1) NaClO (+1)

(bii)

It is a disproportionation reaction which is basically a redox reaction.

(ci)

ClO3- + 2H+ + e ClO2 + H2O E = +1.13V

Ans: O2 + 2H+ + 2e H2O2 E = + 0.08V

(cii)

2 ClO3- + H2O2 + 2H+

(ciii)

H2O2 acts as a reducing agent.

(ai)
(aii)

2 ClO2 + O2 + 2H2O

ClO2 + 4H+ + 5e Cl- + 2 H2O E = + 1.50V

Co(H2O)63+ + e Co(H2O)62+ E = + 1.82V

Ecell = +1.50 (+1.82) = -0.32V
The redox reaction is not spontaneous.
(aiii) Co(NH3)62+ is P
(aiv)
ClO2 + 4H+ + 5e Cl- + 2 H2O E = + 1.50V

Co(NH3)63+ + e Co(NH3)62+ E = + 0.11V

Ecell = +1.50 (+0.01) = +1.39V
Reaction is spontaneous.
ClO2+ 4H+ + 5 Co(NH3)62+

(a)

Cl- + 2 H2O + 5 Co(NH3)63+

-356 = 2 Hf (phosgene) + 2(-92) -2(-134)

Hf (phosgene) = -220 kJ mol-1

(b)
(ci)

This is a free radical reaction which involves UV light.

..

..

:Cl
.. :C:Cl
.. :
x.x.x x
x

(cii)

Angle ClCCl = 120o

(di)

Stage I : Nucleophilic substitution

Stage II: Elimination of HCl

(dii)

Cl

Cl
OH

Cl

HO

Cl

HO
C

Cl

Cl-

(e)

COCl2 + CH3CH2OH
COCl(OCH2CH3) + HCl
Or
COCl2 + 2 CH3CH2OH
COCl(OCH2CH3)2 + 2 HCl

(fi)

Conc. Ammonia in a sealed tube and heat/ethanolic ammonia

(implication of high pressure)

(fii)

Thre are 2N-atoms, each with a lone pair of electrons. If one lone pair of
electrons is used for delocalization together with the carbonyl group, there is
still one pair of electron on N to accept a proton.

(gi)

O.N =(+3)(4)
2(OCNH2)2 + 3 NO2

4CO2 + 8H2O + 7/2 N2

O.N = (-4)(3)
You may multiply the equation by 2
(gii)

It is a (a) photochemical pollutant (smog) (b) toxic gas (c) catalyses acid rain
in industrial zones.

(a)
CH3COCl

Compound C
O
C
O

CH 3

OCH 3

CH2 CH=CH 2

Dilute HNO3

Compound C
OH
O 2N

OCH 3

CH 2CH=CH2

Na

Compound C
O -Na+
OCH3

CH 2CH=CH 3

Tollens reagent

Compound A
CH=CHCOO-

or -COOH

(bi)
OH
Br

OCH3

Br
CH 2CH

CH2

OH

(bii)

COOH
HO

CH 3

(ci)

OCH 3
CH=CHCH 2 OH

(cii)

CH=CHCH 2 OH

CH=CHCHO

LiAlH4/ dry ether

reflux

CH=CHCH 2 OCOCH 3

+ H 2O

Suggested Solns for Nov 2007 Paper 3

1a)
Kp
=
(PCH3CH2CH2CHO) / [(PCH3CH=CH2)(PCO)(PH2)
units

atm-2

b)i)

C3H6 (g) + CO (g) + H2 (g)

40
40
40
-39.6
-39.6
-39.6
0.4
0.4
0.4

CH3CH2CH2CHO
+39.6
39.6

ii)

Kp = (39.6) / (0.4)3 = 618.75 atm-2

iii)

At higher pressure, equilibrium will shift to the right to form more butanal.
Hence formation of butanal is favoured as formation of less number of moles
of gas would reduce the change.

iv)

S has negative sign, as system becomes more orderly with formation of less
number of moles of gas.

v)

G < 0
H - TS < 0
H < TS
S = -ve therefore H = -ve

vi)

Bonds broken (+ve) 6(C-H), (C=C), (C=O), 1(H-H)

Bonds made (-ve) 8(C-H), 3(C-C), (C=O)
H = 2(-410) + 610 + (-740) +436 +3(-350) + 1077 = -487 kJmol-1

ci)

Reaction II: KMnO4 / H+, heat under reflux or K2Cr2O7 / H+, heat under reflux
Reaction III: LiAlH4 in dry ether. Reflux

cii)

PBr3 or PBr5
Conc H2SO4 at 170oC followed by Br2 in CCl4

di)

Comparing C-X bond energies, C-I bond is weaker than C-Br bond. Hence
rate of reaction should be faster for 2-iodobutane.

dii)

2-bromobutane

NaCN
in alc.

CN

LiAlH4

H3C

CH
CH2
NH2

CH2

CH3

Suggested Solns for Nov 2007 Paper 3

H2C
2-bromobutane

CH

Cold

NaOH in

CH2

ethanol

CH3

and
H

H
C

Cold

H3C

CH3

HO

CH2 CH

KMnO4 (aq)

CH2 CH3

OH

H3C

KMnO4 (aq)

CH

CH

OH

OH

e)
1-bromobutane 6/10
2-bromobutane 4/10

There are 10 positions where by the radical can substitute on butane. If a radical
substitute any position marked (a), it will form 1-bromobutane and if a radical
substitutes at position marked (b), 2-bromobutane will be formed.
2a)

graph and explanation lecture notes

general increasing trend / Mg and Al / P and S

b)
Rxn
Add dil HCl to
white powder
Add dil NaOH to
white powder
(separate new
sample)

MgO
dissolves

Observation
Al2O3
dissolves

SiO2
Insoluble

Insoluble

dissolves

dissolves

c)

NaCl + aq
Na+ (aq) + Cl- (aq)
NaCl ionic compound, dissociates completely in water
hydration of ions through ion-dipole interactions. The hydrated ions has low
charge density, no hydrolysis => neutral
PCl5 + 4H2O
H3PO4 + 5HCl
PCl5 is a simple discrete molecule which undergoes hydrolysis giving rise to
acidic solution.

di)

SOCl2 - toxic, corrosive (skin and inhalation hazard)

In the lab, carry out in FUME cupboard.

ii)

H2O + SOCl2
SO2 + H2O

iii)

Few drops of AgNO3(aq)

Few drops of K2Cr2O7 (aq)

SO2 + 2HCl
H2SO3
White ppt of AgCl formed
Ag+ (aq) + Cl- (aq)
AgCl (s)
Orange Cr2O72- turned green Cr3+

CH3

Suggested Solns for Nov 2007 Paper 3

ei)
A

O
C

ii)

OH
O

C
HO

I
II
III

acid base
nucleophilic substitution
hydrolysis

iii)

Reagents and conditions

aq NaOH, heat and distill followed by acidification of salt by dil acid aq
H2SO4
Hf
3ai)

Ca (s)

+178
+

+590 +
1150
Ca2+ (g)

LE
ii)

CaF2 (s)

2F (g)

LE

2(-328)
+

2F- (g)
q+qr+ + r-

Using Hesss Law,

=
=
=

-1220

+158

Ca (g)

Hf

F2 (g)

+178 + 158 +590 + 1150 + 2(-328) + LE

-1220
-2640 kJ mol-1

LE of CaCl2 smaller than that of CaF2

LE is proportional to
Cl- ion larger radius than F- ion therefore LE lower
LE CaO > LE of CaF2
O2- ion has higher charge than F- ion. since LE is directly proportional to
charge of ion therefore CaO > LE of CaF2

b)

CaF2 (s)

i)

Ksp

ii)

=
=
=

Hsoln =
=
=

Ca2+ (aq) + 2F- (aq)

[Ca2+] [F-]2
(2.3 X 10-4) (2 X 2.3 X 10-4)
4.87 X 10-11 mol3dm-9
Hf (product) - Hf (reactant)
[ (-543) + 2(-333) ] (-1220)
11 kJ mol-1

Suggested Solns for Nov 2007 Paper 3

iii)

more soluble in hot water than in cold water as process is endothermic.

ci)

Nature in beryllium nitrate is ionic bonding with covalent character.

Ca(NO3)2 has electrostatic forces of attraction between oppositely charged
Ca2+ and NO3- ions as the melting point is much higher than that of Be(NO3)2

ii)

Mg (NO3)2
MgO + 2NO2 + O2
Ca2+ ion being larger than Mg2+ ion Ca2+ has lower charge density than Mg2+
ion, hence Ca2+ ion less polarizing power, higher temperature needed before
distortion of electron cloud that is decomposition, takes place.

d)

(CH3CO2)2Ca : (HCO2)2Ca
1
:
1

i)

carbonyl compounds formed (CH3)2CO , CH3CHO , HCHO

ii)

(CH3)2CO
CH3CHO
HCHO

Test 1
Reagent
Condition

:
:

CH3CHO, HCHO
(CH3)2CO

2
1
2
aq AgNO3, aq NH3
heat
-

Ag mirror seen
solution remained clear

Test 2
Add H+/KMnO4 to the solutions which gave Ag mirror and heat.
Test vapour given off with aq Ca(OH)2, white ppt is formed by HCHO.
H+(aq) + CN- (aq)

4ai)

HCN

ii)

[H+] [CN-]
[HCN]
-10
4.9 X 10 = [H+]2
0.100
[H+] =
7.00 X 10-6 mol dm-3
Ka =

% molecules ionized =
=
iii)

NaCN

( 7.00 X 10-6 / 0.100 ) X 100

7.00 X 10-3

Na+ (aq) + CN- (aq)

b)(i) order of reaction , order = a,

given rate = k[A]a

(ii) comparing expt 1 & 2

[(CH3)2CO] x 1.2 , relative initial rate x 1.2 , hence 1st order wrt [(CH3)2CO]

Suggested Solns for Nov 2007 Paper 3

Comparing expt 1 &3
[NaCN] x 1.25, relative initial rate x 1.25 , hence 1st order wrt [NaCN]
Comparing expt 3 &4
[(CH3)2CO] x 1.2 , relative initial rate x 1.2 , hence zero order wrt [HCN] as [HCN]
also increase 1.2x but no effect on rate of reaction
Rate = k[(CH3)2CO] [NaCN]
(iii) nucleophilic addition

(iv)- larger steric hindrance that would occur in propanone

- The greater inductive effect of the two CH3 groups lessening the +
charge in the carbonyl carbon
(v) HCN is the Bronsted acid and NaCN provides the CN- intitally (unlike the usual
NaCN as catalyst and HCN as reagent/nucleophile
(c) reactions of optical isomers with non chiral reagents are identical or
Both isomers can lose an H and the OH from adjacent carbon atoms in two
different ways giving the cis or trans product.

Solid NaCN ionizes in solution to give CN- ions. Hence amt of CN- (aq) ions
in solution increase and to reduce this increase position of equilibrium will
shift to the left and hence % of HCN molecules ionized decreases.