ATOMS, MOLECULES & STOICHIOMETRY STRUCTURED/ESSAY ANSWERS

(FUNDAMENTALS)

Question 1
(a) (i) Calculate the empirical formula of Pligots salt.

Taking 100g of salt
K Cr O Cl
Mass/ g 22.4 29.8 27.5 20.3
No. of moles
=
22.4
0.573
39.1
=
29.8
0.573
52.0
=
27.5
1.719
16.0
=
20.3
0.572
35.5

Divide by
smallest no.
1 1 3 1
Simplest
ratio
1 1 3 1

- Empirical formula of Pligots salt is KCrO
3
Cl
(ii) K
2
Cr
2
O
7
+ 2HCl 2KCrO
3
Cl + H
2
O

(b) Cr
2
O
7
2-
+ 14H
+
+ 6e

2Cr
3+
+ 7H
2
O
2Cl

Cl
2
+ 2e

Cr
2
O
7
2-
+ 14H
+
+ 6Cl

2Cr
3+
+ 7H
2
O + 3Cl
2


(VOLUMETRIC ANALYSIS)

Question 2

(a) M
r
of CO
2
= 12.0 + 2(16.0) = 44.0
No of moles of CO
2
given off = 2.20 / (44.0) = 0.05 mol
y = 0.05 / 0.05 = 1
(bi) No of moles of NaOH used = 30.00 / 1000 0.200 = 0.006 mol
No of moles of excess HCl in 25.0 cm
3
of solution = 0.006 mol

No of moles of excess HCl in 250 cm
3
of solution
= 0.006 / 25.0 250 = 0.06 mol

No of moles of HCl used initially = 100 / 1000 3.6 = 0.36 mol
No of moles of HCl that reacted with NiO = 0.36 0.06 = 0.3 mol

NiO + 2HCl NiCl
2
+ H
2
O
No of moles of NiO formed = 0.3 / 2 = 0.15 mol
x = 0.15 / 0.05 = 3
(bii) By balancing of charges,
3(+2) + 1(2) + z(1) = 0
z = 4

(Redox)
Question 3
(a) (i) Mn: From +7 to +2 [Or decrease by 5]
C: From +3 to +4 [Or increase by 1]

(ii) MnO
4
-
+ 8H
+
+ 5e
-
Mn
2+
+ 4H
2
O
C
2
O
4
2-
2CO
2
+ 2e
-
Fe
2+
Fe
3+
+ e
-

3MnO
4
-
+ 24H
+
+ 5C
2
O
4
2-
+ 5Fe
2+
3Mn
2+
+ 5Fe
3+
+ 12H
2
O + 10CO
2

(iii) Number of moles of KMnO
4
= 13.45/1000 x 0.020 = 2.69 x 10
-4
mol
Number of moles of FeC
2
O
4
in 25.0 cm
3
=
3
5
x 2.69 x 10
-4
= 4.48 x 10
-4
mol
Number of moles of FeC
2
O
4
in 250 cm
3
= 4.48 x 10
-4
x 250/25.0
= 4.48 x 10
-3
mol
Concentration of FeC
2
O
4
in the original sample =
3 -
-3
10 x 35
10 x 48 . 4

= 0.128 mol dm
-3

(iv) No. of moles of iron per gram of spinach =
150
10 x 48 . 4
-3
= 2.99 x 10
-5
mol/g

Question 4
(a) (i) Let the oxidation state of vanadium in the fluoride solution be V
n+

4
2 4
MnO
20
n reacted = x 2.50 x 10 mol = 5.00 x 10 mol
1000

MnO
4
+ 8H
+
+5e Mn
2+
+ 4H
2
O
n
e
given out by V
n+
= n
e
taken in by MnO
4
=
4
MnO
5 n


= 5 x 5.00 x 10
4
mol
= 2.50 x 10
3
mol
Since 1.25 x 10
3
mol of V
n+
required 2.50 x 10
3
mol of electrons
Each mole of V
n+
would give out
3
3
2.50 x 10
= 2 mol of electrons
1.25 x 10

Since final oxidation state of V in VO
3
is +5 and 2 moles of electrons were given out
Initial oxidation of V is +5-2 = +3
(ii) 5V
3+
+ 7H
2
O + 2MnO
4
5VO
3
+ 14 H
+
+ 2Mn
2+


ATOMIC STRUCTURE STRUCTURED / ESSAY ANSWERS

Question 1:

(i) Cr: 1s
2
2s
2
2p
6
3s
2
3p
6
3d
5
4s
1
Mn: 1s
2
2s
2
2p
6
3s
2
3p
6
3d
5
4s
2

(ii) 2
nd
IE of Cr: 1590 kJ mol
-1
2
nd
IE of Mn: 1510 kJ mol
-1

2
nd
IE of Cr and Mn involve removal of electron from the 3d and 4s subshell
respectively. Since the 4s subshell is further away from the nucleus than the 3d
subshell, removal of electron from 4s subshell requires less energy.

(iii)

Question 2:
(a) Si
+
(g) Si
2+
(g) + e
(b) 1s
2
2s
2
2p
6
3s
2
3p
2

Energy/ KJ mol
-1
Order of electrons removed
1 4 5 1213

Energy
1s
2s
2p
3s
3p
3d
Correct electronic configuration
Convergence of energy level and
labelled axis

correct shape of graph with correct labels
- Number of protons unchanged nuclear charge unchanged
- As each electron is removed from the atom, the resulting positively charged
ion holds the remaining valence electrons more strongly hence more energy is
required to remove the subsequent electron.
There is a significant increase in ionisation energies between the 4
th
and 5
th
electron
as well as between the 12
th
and 13
th
electron since it involves the removal of
electron from an inner shell .




































CHEMICAL BONDING STRUCTURED/ESSAY ANSWERS
Question 1

(i) CO
2
+ 3H
2
CH
3
OH + H
2
O

(ii) I More energy required to break more extensive hydrogen bonds between
H
2
O molecules compared to less extensive hydrogen bonds
between CH
3
OH molecules.

II More energy required to break stronger hydrogen bonds between CH
3
OH molecules
compared to weaker Van der Waals forces of attraction between CO
2

molecules.


(iii) Shape w.r.t C atom: tetrahedral
Shape w.r.t O atom: bent


Question 2
(i)

(ii) There is a lone pair of electrons on the carbon in the carbon monoxide and
empty d-orbitals in the metal ion. Thus, a dative bond could be formed between
the metal ion and carbon in the carbon monoxide.

(iii) No / the result is not conclusive as hydrogen gas present in the mixture can also
reduce copper oxide to copper.

(iv) Even though CO
2
is non-polar, but it has more electrons than that of CO.
The Van der Waals forces between the CO
2
molecules would be stronger
than the dipole-dipole interactions between CO molecules.

Question 3
(a)
(i) Ethanal: A
Ethanol: C
Propanone: A
2-methylpropane: B


C O
x
x x
x



(ii) Hydrogen bonding between ethanol and water is comparable in strength to the

hydrogen bonding between ethanol molecules and between water molecules.


- - hydrogen bond


+ +


Question 4
(a) (i)

(ii) SO
3

(b) (i)
Both propan-2-ol and ethanoic acid can form intermolecular hydrogen bonds
which are stronger than the intermolecular van der Waals forces of
propanone. Hence less energy required to boil propanone and it has lowest
boiling point.
Ethanoic acid has higher boiling point than propan-2-ol as it can dimerise (by
hydrogen bonds) to give a larger and more polarisable electron cloud, giving
rise to stronger and more extensive intermolecular van der Waals forces
between the dimers which require more energy to overcome.


Question 5
(a)
O
Si
O
O
O
O
Si
O
O
6-

Bond angle ~ 104.5

CH
3
O
H
H
O
H
(b) Zeolite will have a greater affinity for Ca
2+ .
Ca
2+
ion has a
smaller ionic radius and larger charge , therefore the charge density of Ca
2+
is higher
than Na
+
. This results in stronger electrostatic forces of attraction between the
oppositely charged silicate ion and Ca
2+
ion.

(c)
(i) SiO
4
4
+ 2H
2
O SiO
2
+ 4OH

(ii) Water is acting as an acid.

(iii)

Si
O
O
O
O
x
x
x
x
x x
x x
x x
x x
x x
x x
x
x
x
x
x
x
x
x
4-
Tetrahedral around Si atom



























GASEOUS STATE STRUCTURED/ESSAY ANSWERS

Question 1

(i) pV = RT
M
m
r

(7.92 x 10
2
x 1.00 x 10
5
)(0.0213) =
) 0 . 1 0 . 16 0 . 15 ( + +
m
(8.31)(500)
m = 1.30 g

(ii) Strong hydrogen bonding present between CH
3
OH molecules such that the partial pressure
of CH
3
OH was lower than actual.


Question 2
or



Question 3

pV = nRT
32 x 10
3
x 150 x 10
-6
= 0.080/M
r
x 8.31 x 303
M
r
= 42.0

CH
3
COCH
3
CH
4
+ C
2
H
2
O
ketene
M
r
= 42.0
Structural formula: H
2
C=C=O






Pt
CHEMICAL ENERGETICS STRUCTURED/ESSAY QUESTIONS

Question 1
1 (a)
NaCl(s) NaCl(aq)





H
solution =
(409) (414) = +5 kJ mol
1


L.E (NaCl) = H
hydration
(Na
+
) + H
hydration
(Cl

) H
solution

= (390) + (384) (+5)
= 779 kJ mol
1



(b)



















Using Hess Law, E.A (Cl) = 494 122 107 414 (779) = 358 kJ mol
1


(c) Numerical magnitudes of L.E decreases.

Cationic radius of Group I ions increases / interionic distance increases down the group.
Thus, electrostatic forces of attraction between the cation and anion will be weaker.


Question 2

(a)
(100)(4.2)(AT) = AH
c
(
(ethanol) M
ethanol of mass final - 1.00
r
) OR
Na(s) + Cl
2
(g)
414
409
energy /
kJ
m
ol

1

Na(s) + Cl
2
(g)
+107
Na(g) + Cl
2
(g)
+494
Na
+
(g) + Cl
2
(g)
+(244)
Na
+
(g) + Cl(g)
0
Na
+
(g) + Cl

(g)
E.A (Cl)
NaCl(s)
414
779
(100)(4.2)(T
max
T
i
) = AH
c
(
46.0
m - 1.00
f
)

(b) 1. Measure the initial temperature of water, T
i
.
2. Heat the water until AT = 50
o
C / T
max
= 75
o
C
3. Record the maximum temperature of water, T
max
(and determine the change in temperature
AT = T
max
T
i
)
4. Reweigh the spirit burner to determine the final mass of ethanol. (Calculate the change in
mass of ethanol in the spirit burner.)

(c) Ethanol is highly flammable.

Spirit burner should be covered when not in use / Avoid heat, sparks and flame near the ethanol
when not in use.

(d) Less exothermic due to heat loss to the surrounding / incomplete combustion / heat capacity of
beaker is not considered.


Question 3

(i) Sr(OH)
2
(aq) + 2HCl(aq) SrCl
2
(aq) + 2H
2
O(l)

(ii) Standard enthalpy change of neutralisation (AH
n
u
) is the energy released /
enthalpy change when an acid and a base react to form one mole of water
under standard conditions of 298K and 1 atm.

(iii) Actual quantity of heat evolved =
80
100
[(50+50) 4.2 8.5]
= 4463 J
2HCl(aq) + Sr(OH)
2
(aq) SrCl
2
(aq) + 2H
2
O(l)
n
H2O
formed = 2 x n
Sr(OH)2
reacted
= 2 x
1000
50
x 0.77
= 0.077 mol
H

n
=
077 . 0
4463
(e.c.f.)
= 58.0 kJ mol
-1


(iv) Dilute ethanoic acid is a weak acid which dissociates incompletely in aqueous
solution.
Some of the energy evolved from the neutralization reaction is used to dissociate
the weak acid completely.




(c)


Question 4

(i)
AG = AH - TAS
AS =
T
G - H

=
298
65.4 - 131

= +0.220 kJ mol
-1
K
-1
or +220 J mol
-1
K
-1


The standard entropy change is positive since the number of gaseous
molecules increases after the reaction.
(ii) Since S is also positive, G will become more negative / less positive when the
temperature increases.
Thus an increase in the temperature will make this reaction more spontaneous
(or vice versa).






Question 5
(a)


(bi) Entropy is a measure of the disorder/randomness of matter and energy of a system.

(bii) AS
o
= 69.91 + 26.8 63.24
= +33.5 J K
-1
mol
-1

(biii) AG
o
= AH
o
- TAS
o

= +37.1 298(
1000
33.5
)
= +27.1 kJ mol
-1

Since AG
o
> 0, reaction II is not spontaneous under room conditions.

(c) There is a reduction in number of moles of gaseous molecules and the system
becomes more orderly.
Thus AS < 0 or the entropy of the system decreases.

(d)
+
+
+

r r
q q
energy Lattice

MgO will have a larger magnitude of lattice energy compared to MgF
2
.
This is because q
+
and r
+
are the same for both compounds, but charge of O
2-
ion is
twice that of F
-
ion (while the size of O
2-
is only slightly larger).


Question 6
(i)
No of moles of propane =
3.1
44
= 0.0705 mol
Heat released from combustion = 0.0705 x 2219 = 156 kJ
Specific heat capacity of water =
3
156 10
500 (100 25)

= 4.17 J K
-1
g
-1
(ii) Standard enthalpy change of combustion is the heat energy released when 1 mole of
the substance is completely burnt in oxygen at 298 K and 1 atm.
(iii)
Heat released from combustion = 500 x 4.17 x (80-25) = 115 kJ
No of moles of butane burnt =
2.5
58
= 0.0431 mol
Enthalpy change of combustion of butane =
115
0.0431
= 2668 kJ mol
-1
(iv)
There was heat loss from the flame and the heated beaker of water to the surroundings
resulting in a lower experimental value of AH
c
.
Or
There was incomplete combustion of the butane resulting in a lower experimental value
of AH
c
.
Or
Heat capacity of calorimeter has been ignored, resulting in a lower experimental value of
AH
c
.

(v)









By Hess law,
AH
r
+ (2877) = 2717 + (286)
AH
r
= 126 kJ mol
-1


Question 7

(i) From methane to pentane an additional CH
2
- needs to be burned, therefore
increasingly more heat is given out.

(ii) moles of methane burnt = 9.0 x 10
10
/24 = 3.75 x 10
9
mol
Heat produced from burning methane = 3.75 x 10
9
x 890 kJ = 3.34 x 10
12
kJ
Heat absorbed by water, in J =

x 3.34 x 10
12
x 1000 = 2.50 x 10
15
J
2.50 x 10
15
= mcAT
m, mass of water = 2.50 x 10
15
/(4.18 x 80) = 7.48 x 10
12
g



Question 8
(a)
(i) CH
3
CH
2
OH(l) + 3O
2
(g) 2CO
2
(g) + 3H
2
O(l) [
Enthalpy change of reaction is the energy evolved when 1 mol of ethanol is
completely burnt in excess oxygen under standard conditions.

(ii) H
c
= [BE(C-C) + BE(C-O) + 5BE(C-H) + BE(O-H) + 3BE(O=O)] [4BE(C=O)
+ 6BE(O-H)]
= (350 + 360 + 5(410) + 460 + 3(496)) (4(740) + 6(460))
= -1010 kJ mol
-1
(3 s.f.)

(iii) The bond energies values given in the Data Booklet are just average values.
or Bond energies are based on calculations from reactions in the gas phase.
However ethanol and water are in the liquid state.





























CHEMICAL EQUILIRBIUM STRUCTURED/ESSAY ANSWERS

Question 1

(a) (i) I
By Le Chateliers principle, the equilibrium will try to decrease the temperature by
favouring the backward endothermic reaction to remove the excess heat

II
Position of equilibrium will not shift / remain the same due to the same number of
moles / stoichiometric ratio for gaseous molecules for the reactants and products
(ii)

The carbonoxygen triple bond in CO is stronger than the single and double
carbonoxygen bonds in the Data Booklet.

(iii) H
2
O(g) + CO(g)

CO
2
(g) + H
2
(g)
Initial / atm
A / atm +2.12 +2.12
Eqm / atm 2.12 2.12


K
p
=
CO O H
H CO
p p
p p
-
-
2
2 2


p
H2O
+ p
CO
= 5 2(2.12) = 0.76 atm

Since steam and CO were added in equimolar amount,

p
H2O
= p
CO
=
2
76 . 0
= 0.38 atm

Substituting the equilibrium partial pressures,

K
p
=
CO O H
H CO
p p
p p
-
-
2
2 2
=
2
2
) 38 . 0 (
) 12 . 2 (
= 31.1

(iv) Bubble the product gas stream into NaOH solution.

CO
2
gas is acidic and will react with the NaOH solution. H
2
gas is neutral and thus
no reaction.

Question 2
(a) (i)
pV = nRT
n =
RT
pV

C O
x
x
x
x
C O
x
x
x
x
=
273) + (327 x 31 . 8
) 10 x (2.96 x ) 10 x 01 . 1 (
-3 5

= 0.0600 mol

(ii) Number of moles of steam before reaction = 0.900 / 18.0
= 0.0500 mol
H
2
O(g) + C(s) H
2
(g) + CO(g)
Initial/ mol 0.0500 0 0
Change/ mol -x +x +x
Equilibrium/ mol 0.0500 - x x x

Total number of moles = 0.0500 - x +x +x = 0.0500 + x =0.0600 mol
Thus x = 0.0100 mol
Percentage of steam reacted = 0.0100 / 0.0500 x 100%
= 20%
(iii) K
p
=
O H
CO H
2
2
p
p x p


=
) 00 . 1 x
0600 . 0
0400 . 0
(
) 00 . 1 x
0.0600
0.0100
( x ) 00 . 1 x
0600 . 0
0100 . 0
(

= 0.0417 atm
b(i) K
p
remains the same
since it only depends on the temperature and the temperature is unchanged.

(ii) Percentage of steam that has been reacted remains the same
since the partial pressures of H
2
O, CO and H
2
are not affected.

Question 3
(a) Wear gloves when handling CHCl
3
as it is corrosive. Perform in fume
cupboard. Wear safety goggles.
(b) (i) [I
2
] in aq layer = 1.680/130
= 0.0129 mol dm
3
(ii) [I
3

] in aq layer = 0.735 0.01292

= 0.722 mol dm
3
(c)
[I

] in aq layer = 0.810 0.722

=0.088 mol dm
3

K
C
= [I
3

]/[I
2
] [I

]
= 0.722/(0.0129)(0.088)
= 636 mol
1
dm
3

(d) sp
3

IONIC EQUILIBRIUM STRUCTURED/ESSAY ANSWERS

Question 1
1 (a) (i)
n(lactic acid) = 15 . 0
1000
0 . 10
= 1.50 x 10
3
mol
n(NaOH) = n(lactic acid) = 1.50 x 10
3
mol
Volume (NaOH) for neutralisation = 1000
10 . 0
10 50 . 1
3

= 15 cm
3


(ii) At maximum buffer capacity, pH = pK
a


K
a
= 10
3.86
= 1.38 x 10
4
mol dm
3



(iii)
1.38 x 10
4

) 15 . 0 (
] [
2 +
H

[H
+
] = 4.55 x 10
3
mol dm
3


pH = 2.34

(b) (i) CH
3
CH(OH)CO
2

+ H
2
O CH
3
CH(OH)CO
2
H + OH




(ii)
[sodium lactate] =
0 . 25
15 . 0 0 . 10
= 0.0600 mol dm
3


(iii)
K
b
=
4
14
10 38 . 1
10

= 7.25 x 10
11
mol dm
-3

7.25 x 10
-11


) 0600 . 0 (
] [
2
OH


[OH

] = 2.09 x 10
6
mol dm
3


pH = 14 lg (2.09 x 10
6
) = 8.32


(c) (i) K
sp
= [Ca
2+
][C
3
H
5
O
3

]
2


K
sp
= (0.0157)(2 x 0.0157)
2
= 1.55 x 10
5
mol
3
dm
9



(ii)
Ionic product = |
.
|

\
|

150
100
2 . 0
2
150
50
1 . 0 |
.
|

\
|
= 1.48 x 10
4
mol
3
dm
9


Since ionic product > K
sp
, a white precipitate is formed.

Question 2
(a) (i) RCOOH RCOO
-
+ H
+

Initial concentration 0.050 0 0
Change in concentration -x +x +x
Final concentration 0.050 x +x +x
K
a
=
| || |
| | RCOOH
H RCOO
+
=
x 0.050
x
2

0.050
x
2
(assuming x << 0.050)
x =
3
0.050x10

= 0.007071
pH = -lg 0.007071
= 2.15

(ii)

Ba(OH)
2
+ 2RCOOH (RCOO
-
)
2
Ba
2+
+ 2H
2
O
mole of RCOOH = 0.050 x
1000
20
= 0.001
mole of Ba(OH)
2
reacted = (0.001) = 0.0005
initial mole of Ba(OH)
2
= 050 . 0
1000
40
x = 0.002
excess mole of Ba(OH)
2
= 0.002 0.0005 = 0.0015
number of mole of excess OH
-
= 0.003
pOH = -lg 0.05 = 1.301
pH = 14 1.301 = 12.7

(iii) I do not agree with the statement.
The pH of the salt is greater than 7 due to the hydroxide ion that is formed from the
salt hydrolysis of RCOO-.
RCOO
-
+ H
2
O RCOOH + OH
-

(iv)
















Question 3
(a) (i) BaSO
4
(s) Ba
2+
(aq) + SO
4
2-
(aq)
By Le Chateliers Principle, when potassium sulfate is added, the equilibrium
will shift to the left to decrease the concentration of sulfate ions . This is to
reduce the solubility of barium sulfate as barium ions are poisonous.
(ii) mole of Ba(NO
3
)
2
=
6 16 2 4 1 137
0.011
+ +
= 4.215 x 10
-5

= mole of Ba
2+

mole of MgSO
4
= 0.050 x 0.2 = 0.01


new concentration of Ba
2+
=
050 1
10 215 4
5
.
.

= 4.014 x 10
-5
mol dm
-3


new concentration of SO
4
2-
=
050 1
001 0
.
.
= 9.524 x 10
-3

K
sp
= [Ba
2+
][SO
4
2-
]
= (4.014 x 10
-5
)(9.524 x 10
-3
)
= 3.82 x 10
-7
mol
2
dm
-6


(iii) Let the solubility of barium sulfate in the solution be x.
BaSO
4
Ba
2+
+ SO
4
2-

Initial concentration x 6 x 10
-3
0
Change in concentration -x +x +x
Final concentration 0 6 x 10
-3
+x +x
K
sp
= [Ba
2+
][SO
4
2-
]
3.82 x 10
-7
= (6 x 10
-3
+x)(x)
(6 x 10
-3
)(x) (assuming x << 6 x 10
-3
)
x = 6.37 x 10
-5
mol dm
-3
or 6.30 x 10
-5
mol dm
-3
(for ans without assumption)
















INTERGRATED QUESTION

Piperidine, C
5
H
11
N, is a colourless fuming liquid with an odor described as pepper-like
and widely used as a chemical reagent in the synthesis of organic compounds,
including pharmaceuticals.
The chemical structure of piperidine is shown below.



piperidine

Piperidine is a weak Bronsted base.

(a) A weak Bronsted base is a species which accepts protons (H
+
) from an acid and
is only partially dissociated in aqueous solution.
Piperidine and its conjugate acid are in equilibrium in aqueous solution.
C
5
H
11
NH
+
C
5
H
11
N + H
+


(b) C
5
H
11
N + H
2
O C
5
H
11
NH
+
+ OH
-



(c)
(i)
K
b
=
] N H C [
] OH ][ NH H C [
11 5
- +
11 5


pOH = 14 11.4
= 2.6

[OH
-
] = 10
-2.6

= 2.52 x 10
-3
mol dm
-3

C
5
H
11
N + H
+
C
5
H
11
NH
+
K
b
=
)
3
2
(
) 10 x 52 . 2 )(
3
1
(
3 -

= 1.26 x 10
-3
mol dm
-3

(ii) C
5
H
11
N + H
+
C
5
H
11
NH
+

Large reservoir of undissociated C
5
H
11
N molecules remove added H
+
to form
C
5
H
11
NH
+
. Thus, the pH of solution is almost constant and the colour of solution
remains blue.
C
5
H
11
NH
+
+ OH

C
5
H
11
N + H
2
O
Large reservoir of C
5
H
11
NH
+
from the salt remove added OH

to form C
5
H
11
N and
neutral water. Thus, the pH of solution is almost constant and the colour of
solution remains blue.

(ii) No. of moles of C
5
H
11
N =
0 . 85
10
= 0.118 mol
[C
5
H
11
N] =
3 -
10 x 150
118 . 0
= 0.787 mol dm
-3

1.26 x 10
-3
=
787 . 0
] OH [
2 -
(e.c.f.) (Accept if 1.26 x 10
-3
= [OH
-
]
2
/(0.787 [OH
-
])
[OH
-
] = 0.0315 mol dm
-3
[OH
-
] = 0.0309 mol dm
-3

pH = 14 + lg(0.0315) = 12.5 pH = 12.5

(iv) C
5
H
11
N + HNO
3
C
5
H
11
NH
+
NO
3
-

No. of moles of HNO
3
required = 118 . 0 x
150
0 . 25
(e.c.f.)
= 0.0197 mol
Volume of HNO
3
required = 0.0197 x 1000
= 19.7 cm
3

(v)
















Indicator: Methyl orange

(d) Hydrolysis of CO
3
2-
occurs.
CO
3
2-
+ H
2
O HCO
3
-
+ OH
-

C
5
H
11
N + H
2
O C
5
H
11
NH
+
+ OH
-
------ eqm 1
By Le Chateliers Principle, the increase in [OH
-
] resulting from the hydrolysis of
CO
3
2-
causes the eqm 1 to shift left to lower the [OH
-
].
Thus, degree of dissociation of C
5
H
11
N decreases.
K
b
of C
5
H
11
N remains unchanged as it is only affected by temperature.
19.7 V
HNO3
/ cm
3
Buffer 12.5
pH
(e)
(i) Piperidinium nitrate has a giant ionic structure made up of C
5
H
11
NH
+
and NO
3
-
ions held together by strong ionic bonds.
Piperidine has a simple molecular structure made up of C
5
H
11
N molecules held
by intermolecular hydrogen bonding.

More energy is required to overcome the stronger ionic bonds (or less energy is
required to overcome the weaker hydrogen bonding). Thus, piperidinium nitrate
has a higher melting point than that of piperidine.

(ii)







(f) 2OC
4
H
8
NH + H
2
SO
4
2(OC
4
H
8
NH
2
)
+
+ SO
4
2-

H
2
SO
4
+ 2NaOH Na
2
SO
4
+ 2H
2
O
No. of moles of NaOH = [(34/1000) x 0.025]
= 8.50 x 10
-4
mol

No. of moles of H
2
SO
4
remaining = 8.50 x 10
-4
/ 2
= 4.25 x 10
-4
mol

No. of moles of H
2
SO
4
reacted = [(100/1000) x 0.0100] 4.25 x 10
-4

= 5.75 x 10
-4
mol

No. of moles of OC
4
H
8
NH in 0.1 cm
3
= 2 x 5.75 x 10
-4

= 1.15 x 10
-3
mol













INTRO TO ORGANIC CHEMISTRY STRUCTURED/ESSAY ANSWERS

Question 1
(a)





(b)


Question 2

(ai) CH
3
CO
2
C
2
H
5



(aii) H
2
C=C=O
1 2
C1: sp
2
, trigonal planar, 3 sigma bonds and 1 pi bond
C2: sp, linear, 2 sigma bonds and 2 pi bonds

(bi) Optical Isomerism

Mirror




CH
3
CH
3
CH
2
C
H
Cl
CH
3
CH
3
CH
2
C
H
Cl


(bii) A racemic mixture is obtained.
Intermediate alkyl radical

1

is trigonal planar with respect to carbon 1.

Chlorine radical attacks above and below the planar structure with respect to
carbon 1 with equal probability.
































CH
3
CH
2
CHCH
3
HYDROCARBONS-ALKANES STRUCTURED/ESSAY ANSWERS

Question 1

(a) (i) uv light / heat

(ii) Name: Free radical substitution

C
2
H
6
Cl
2
uv / heat
2Cl
Initiation:
Propagation: Cl
+ HCl
+ Cl
2
+
Cl
+ C
2
H
5
Cl
Termination: 2Cl Cl
2
Cl
+
C
2
H
5
Cl
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
2CH
3
CH
2
CH
3
CH
2
CH
2
CH
3


(iii) C
2
H
6
+ X
2
C
2
H
5
X + HX

AH = [BE(CH) + BE(XX)] [BE(CX) + BE(HX)]

AH = (410 + 244) (340 + 431) = 117 kJ mol
1
(when X = Cl)
AH = (410 + 193) (280 + 366) = 43 kJ mol
1
(when X = Br)

(iv) Weak HI (299 kJ mol
1
) and CI bonds (240 kJ mol
1
) are formed.

AH
reaction
is likely to be endothermic as less energy is evolved so no reaction occurs with
iodine.

(b) (CH
3
)
2
CHCH
2
Cl : (CH
3
)
2
CClCH
3
= 9 : 1
as ratio of primary hydrogens : tertiary hydrogen = 9 : 1

OR

(CH
3
)
2
CHCH
2
Cl : (CH
3
)
2
CClCH
3
< 1 : 1
as primary radical is much less stable than tertiary radical

Question 2

(ai)






C C H
H
H
H
Cl
Cl
C C H
H H
H
Cl Cl

(aii) Free Radical Substitution Mechanism
Initiation:



Propagation:



















Termination (any 1):








(aiii) This is a chain reaction. Covalent bond in chlorine easily broken. Once
chlorine radical is formed, more radicals can be generated in the propagation
steps.


Cl Cl 2 Cl
CH
3
C
H
H
H +
HCl
Cl CH
3
CH
2
+
Cl
CH
3
CH
2
+ Cl
2
CH
3
CH
2
Cl +
Cl CH
3
C
H
H
Cl
+
CH
3
CHCl +
HCl
Cl
2
+
+ HCl
CH
3
CHCl
CH
3
CHCl
2
Cl CH
3
CH
2
Cl
+
Cl 2 Cl
2
+
CH
3
CHCl CH
3
CHCl
2
2
Cl
CH
3
CH
2
CH
3
CH
2
CH
2
CH
3
CH
3
CH
2
2 CH
3
CHCl CH
3
(CHCl)
2
CH
3

Cl -

(b) Q is R is S is








Question 3

(ai) Type of reaction: Free Radical Substitution


(aii) Ratio of 1bromo to 2bromo to 3bromo is 3 : 2 : 1


(aii)
CH
3
CH
2
CH
2
CHCH
2
Br
CH
3
CH
2
CH
2
CHBrCH
2
Br
Br
2 +
+ Br
CH
3
CH
2
CH
2
CHCH
2
Br + Br CH
3
CH
2
CH
2
CHBrCH
2
Br Or



(bi) Type of isomer: Structural (or chain) isomers

(bii) X is 2,2-dimethylpropane or CH
3
C(CH
3
)
2
CH
3

(biii)













CH
3
CH CHCH
3
CH
3
CH
3
C
CH
3
CH
CH
3
CH
3
CH
3
Br
CH
3
CH CHCH
2
Br
CH
3
CH
3
HYDROCARBONS-ALKENES STRUCTURED/ESSAY ANSWERS

Question 1
(i) I type of reaction: elimination of HBr

II type of reaction: oxidation / oxidative cleavage

(ii) C
7
H
14
+ 3[O] (CH
3
)
2
CHCOCH
3
+ CH
3
CO
2
H

(iii)






(b)


Number of stereoisomers = 2
2
= 4




Question 2

(a) No. Styrene has a simple molecular / simple covalent structure with intermolecular van
der Waals forces of attraction (induced dipoleinduced dipole).
It is insoluble in water because no favourable interactions between styrene and water
molecules can be formed as the weak intermolecular van der Waals forces of attraction in
styrene are not able to displace the strong intermolecular hydrogen bonds in water for
solvation/hydration to occur.

(bi) Reagent: H
2
O (g) or steam
Conditions: heat in the presence of H
3
PO
4
catalyst at 300
o
C and 70 atm

Major product:
or


(bii) Type of stereoisomer: Optical isomers or Enantiomers

*asterix is optional since it is not stated in question

(biii) Name of mechanism: Electrophilic Addition
Mechanism:
Step 1

- The t electron cloud of styrene polarises the BrBr bond and induces a dipole in
the bromine molecule.
- The electrophile (Br
+
) attacks the carboncarbon double bond to form an unstable
cyclic cation intermediate and bromide ion, Br

.


Step 2

- Bromide ion attacks the unstable cation intermediate from the opposite side to form
the stable addition product (1,2dibromoethane).

(ci) - Both have simple molecular / simple covalent structure.
- Boiling styrene and limonene involves breaking the weak intermolecular
van
der Waals forces (induced dipole-induced dipole).
- However, limonene has stronger intermolecular van der Waals forces
due to its larger size (as seen from larger molar mass) and thus has a larger
electron cloud which is easier to polarise.
- Hence, more energy is required to boil limonene.

(cii) pV= (m/M)RT
p = (mRT)/VM

Mass of limonene = 28 cm
3
x 0.8411 g cm
3

= 23.5508 g

Partial pressure of limonene = (23.5508 x 8.31 x 328) / (2.5 x 10
3
x 132.2)
= 194226 Pa
= 1.94 x 10
5
Pa (3sf)
Mass of styrene = 32 cm
3
x 0.909 g cm
3

= 29.088 g
Partial pressure of styrene = (29.088 x 8.31 x 328) / (2.5 x 10
3
x 104.2)
= 304355 Pa
= 3.04 x 10
5
Pa (3sf)




(di)

C H
3
OH
OH
C H
3
CH
2
OH
OH


(dii)

O
CH
3
CH
3
O
O
OH
and
C O O