1

AJC BT1 2013 9647/02/H2 [Turn over

ANDERSON JUNIOR COLLEGE

Block Test 1 2013 (modified)


NAME:______________________________ PDG:__________ Register No: _____



CHEMISTRY
9647/02
Higher 2

8 January 2013
Paper 2 Structured Questions

1 hour 30 minutes

Candidates answer on the Question Paper.
Additional Materials: Data Booklet


































This document consists of 13 printed pages.
Topics Tested:
Chemical Energetics
Chemical Equilibria
Ionic Equilibria
Chemical Periodicity
Reaction Kinetics
All Organic Chemistry until Arenes

IMPORTANT! Please read this first!

You need to revise on the topics first so that you can use this
paper to consolidate your learning and find out which are the
topics that you need to further work on.
Please attempt this paper as a time trial, noting the time given
(as indicated above) to complete it.
Before you attempt the questions, check that you have the
following:
Data Booklet
Calculator

2
AJC BT1 2013 9647/02/H2 [Turn over

1 When fuel consisting of 2,3,4trimethylpentane, C
8
H
18,
is combusted in a car engine, it can form
either CO
2
or CO, according to the following equations.
C
8
H
18
(l) +
2
25
O
2
(g) 8CO
2
(g) + 9H
2
O(l) --------------------------------------- (1)
C
8
H
18
(l) +
2
17
O
2
(g) 8CO(g) + 9H
2
O(l) --------------------------------------- (2)
The following data are available:
Reaction H
o
/ kJ mol
1
S
o
/ J mol
1
K
1

(1) 5465 553
(2) 3261 +138

(a) (i) Calculate G
o
for reactions (1) and (2).












G
o
for reactions (1) ..

G
o
for reactions (2) ..

(ii) Hence, suggest, with reason, which reaction predominantly takes place during the
combustion of C
8
H
18
under standard conditions.





(iii) On the axes provided below, sketch how G for each reaction (1) and (2) will vary
with temperature. Label your sketches appropriately.













G / kJ mol
1




0
T / K
3

AJC BT1 2013 9647/02/H2 [Turn over
(iv) Comment on whether CO or CO
2
will be produced when combustion takes place at
very high temperatures.




[7]

(b) 2,3,4trimethylpentane can react with chlorine via free radical substitution to produce a
mixture of four monochlorinated products.

(i) Draw the structural formula of the four monochlorinated products formed from
2,3,4trimethylpentane.



















(ii) For 2,3,4trimethylpentane, the order of reactivity of tertiary and primary hydrogen
atoms follows a 5:1 ratio.

Predict the ratio in which the products you have drawn in (b)(i) are formed.



















[6]
[Total: 13]
4

AJC BT1 2013 9647/02/H2
2 (a) But1ene and hydrogen chloride react together according to the equation:

CH
2
=CHCH
2
CH
3
(g) + HCl(g) CH
3
CHClCH
2
CH
3
(g) H < 0

To study the kinetics of this reaction, two students carried out their own different sets of
experiments and obtained the following graphs.















(i) Use Student A's graph to deduce the order of reaction with respect to but1ene.





(ii) Explain why the halflife of but1ene in Student B's graph is not constant.





(iii) Given that the reaction is first order with respect to HCl, write the rate equation for the
reaction, in terms of partial pressures.



(iv) Determine the value of the rate constant, k, for the reaction.






value of the rate constant, k .

(v) Deduce the halflife of but1ene when the partial pressure of HCl is halved in
Student As experiment.






halflife of but1ene .
[5]
0
0
but1ene
but1ene
5

AJC BT1 2013 9647/02/H2 [Turn over
(b) (i) Describe the mechanism for the reaction between but1ene and HCl to produce
CH
3
CHClCH
2
CH
3
.






















(ii) Sketch the energy profile diagram of the reaction between but1ene and HCl. Label
clearly the activation energy and enthalpy change of the reaction.

















(iii) Explain why the product formed in this reaction does not exhibit optical activity.






[6]





6

AJC BT1 2013 9647/02/H2
(c) Draw the structures of the organic products formed from the following reactions. The
molecular formula of the product formed in (c)(v) is given.

(i)
cold acidified KMnO
4




(ii)
hot acidified KMnO
4




(iii)
hot alkaline KMnO
4




(iv)
CH
3
conc HNO
3
, conc H
2
SO
4




(v)

OH
Br
2



C
5
H
9
OBr
[6]
[Total: 17]



7

AJC BT1 2013 9647/02/H2 [Turn over
3 (a) Many chemists have contributed to the development of the Periodic Table. John Newland
was one of the first few chemists who attempted to classify elements in a systematic way,
based on atomic weight. Part of Newlands Periodic Table is shown below.

Row 1
5
B
6
C
7
N
8
O
Row 2
9
F
11
Na
12
Mg
13
Al
14
Si
15
P
16
S
Row 3
17
Cl
19
K
20
Ca
24
Cr
22
Ti
25
Mn
26
Fe

On each of the grids below, sketch the general trends of the properties of the elements
across Row 2 of Newlands Periodic Table.

(i)

(ii)


(iii)

(iv)

[4]
(b) Aluminium oxide is amphoteric.

Write two equations that illustrate the amphoteric behavior of aluminium oxide and state
which reaction is typical of a metal and which is typical of a nonmetal.

Behaves like a

Equation 1:

Equation 2:
[2]
Electrical conductivity of elements
8

AJC BT1 2013 9647/02/H2
(c) On crossing the second and third periods, the chlorides of the elements change in structure
and in their reactions with water.

(i) 0.1 mol each of the four chlorides below is separately added to 1 dm
3
of water.

Sketch a graph showing the variation in pH of these resulting solutions.















(ii) Account for the pH of the aqueous solutions of carbon tetrachloride and phosphorus
pentachloride. Write balanced equations for the reactions, if applicable.

..

..

..

..
[4]
[Total: 10]
























pH
7
NaCl AlCl
3
CCl
4
PCl
5

9

AJC BT1 2013 9647/02/H2 [Turn over
4 In a typical laboratory, gas phase reactions are difficult to control and hence not common.
Industrial production utilising gas phase reactions are similarly difficult to control and typically only
used for manufacture of organic chemicals, sulfuric acid (Contact process) or ammonia (Haber
process).

The Contact process used to produce sulfuric acid involves a threestage process. Using V
2
O
5

as a catalyst, reaction II achieves 99.5% conversion of sulfur dioxide to sulfur trioxide. The
essential reactions are as follows:

I: S(g) + O
2
(g) SO
2
(g) H = 308 kJ mol
1

II: 2SO
2
(g) + O
2
(g) 2SO
3
(g) H = 192 kJ mol
1

III: SO
3
(g) + H
2
O(l) H
2
SO
4
(l) H = 130 kJ mol
1


(a) Write an expression each for K
c
and K
p
of reaction II.
























[2]

































10

AJC BT1 2013 9647/02/H2
(b) The following graph shows how the concentration of SO
3
varies with time in reaction II.
















(i) A change in condition was introduced to the reaction mixture at t
1
such that the
concentration of SO
3
increases at a different rate after t
1
.

The dotted line in the graph above illustrates how the concentration of SO
3
would vary
with time if no change in condition was introduced at t
1
.

Suggest what this change could be and explain your answer.

.......

.......

.......

(ii) The equilibrium mixture at t
2
was suddenly heated to a higher temperature.

Sketch on the graph above to show how the concentration of SO
3
would change from
t
2
till equilibrium is reached.

(iii) Suggest and explain whether reaction II should be conducted at high or low pressure.

.......

.......

.......
[4]
[Total: 6]


concentration
of SO
3

time
t
1
t
2
0
11

AJC BT1 2013 9647/02/H2 [Turn over
5 (a) Tartaric acid, C
4
H
6
O
6
, (can be represented as H
2
T) is a dibasic acid with the following
structure.

HO
O
OH
O
OH
OH


At 298 K, K
a1
and K
a2
of tartaric acid are 1.05 x 10
3
mol dm
3
and 4.57 x 10
5
mol dm
3

respectively and it can ionise in stages.


H
2
T
HT T
2
H
+
H
+
pK
a1
pK
a2


(i) Write an expression for K
a1
of tartaric acid.


.......

(ii) Explain why K
a2
is smaller than K
a1
.

.......

.......
[2]

(b) 40 cm
3
of a 0.30 mol dm
3
tartaric acid was titrated with a 0.6 mol dm
3
NaOH at 298 K.

(i) Calculate the volume of NaOH required for complete neutralisation of tartaric acid.
Hence calculate the concentration of the salt solution formed.
























volume of NaOH required

concentration of the salt solution formed
12

AJC BT1 2013 9647/02/H2
(ii) Write an equation to show why the pH at the second equivalence point of the titration
is greater than 7.

.......

(iii) Calculate the pH at the second equivalence point.


















pH at the second equivalence point

(iv) Using the data given above and your answers to (b)(i) and (iii), sketch the pHvolume
added curve of this titration.














[8]

(c) Potassium hydrogen tartrate, KHC
4
H
4
O
6
, (can be represented as KHT) is a potassium salt
of tartaric acid, which occurs naturally in grapes.

K
+
O
-
O
OH
O
OH
OH

Unlike most potassium salt, potassium hydrogen tartrate has a relatively low solubility.




13

AJC BT1 2013 9647/02/H2 [Turn over
In an experiment conducted at 25
o
C, solid potassium hydrogen tartrate is first
dissolved in pure water until no more solid dissolves. The excess solid is then filtered
off to give a saturated solution. The solubility of potassium hydrogen tartrate at 25
o
C
was found to be 0.0328 mol dm
3
.

(i) Write an expression for the solubility product of potassium hydrogen tartrate.







(ii) From the data given on page 16, calculate a value for K
sp
of potassium hydrogen
tartrate at 25
o
C and state its units.








K
sp
of potassium hydrogen tartrate ...

(iii) The saturated solution is now heated to 30
o
C in a water bath. Concentrated aqueous
KNO
3
is then added dropwise to the heated solution.

The value of the K
sp
of potassium hydrogen tartrate at 30
o
C is 1.58 x 10
3
.

Determine the concentration, in mol dm
3
, of K
+
ions present when the first trace of
precipitate appears. State any assumption you have made.




















Assumption ..
[4]
[Total: 14]