J1 Promos 2016 Paper 2 Answers

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Anderson Junior College

H1 Chemistry 8872 2016 JC1 Promo Paper 2 Suggested Solutions

1 (a) (i) Ca(OH)2 + CO2 CaCO3 + H2O [1]

n(C) present in A = n(CO2)


= n(CaCO3)
10.0
=
100 .1
= 0.0999 mol

n(H) present in A = 2 x n(H2O)


1 .8
= 2( )
18.0
= 0.200 mol

Empirical formula is CH2

(ii) Let the molecular formula of A be CnH2n. [1]


224 = n(12.0 + 2 x 1.0)
n = 16

Molecular formula is C16H32

Comments:
For (i), most students could determine the nCO2 and nH2O to be 0.0999 and 0.1 respectively, but not
all could thereafter show that the C : H ratio as 0.0999 : 0.2. It is disappointing that many had
difficulty seeing this ratio as approximately 1:2.
Credit for (ii) was given as long as students displayed a correct concept in their working. Students
should have persevered to display their understanding of the concept of ‘n x (Mr of empirical
formula) = Mr’, even though their previous answer may be wrong.

(b) 70 [1]
n(CO2) =
24
= 2.92 mol

1
n(A) combusted = x 2.92
16
= 0.182 mol

Minimum mass of hydrocarbon A combusted = 0.182 x (16 x 12.0 + 32 x 1.0)


= 40.8 g (3 s.f.)

Comments:
Many students did not recognise that the gas produced is just CO2. H2O produced is not a gas as
measurements are taken at r.t.p. H2O would have been a liquid at 298 K.

(c) (i) y y [1]


CxHy + (x + ) O2 xCO2 + H2O
4 2

©2016AndersonJC/CHEM 1
(ii) volume of CO2 = 60 cm3
n(CO 2 ) x

n(C xHy ) 1
V(CO 2 ) x

V(C xHy ) 1
60 x

20 1
x=3 [1]

(VCxHy + VO2, reacted + VO2, unreacted) – (VCO2 + VO2, unreacted)= Vcontraction


y
20 + 20(3 + ) – 60 = 60
4
y=8 [1]

Molecular formula of hydrocarbon B is C3H8.

Comments:
For (i), majority could state the products of combustion of hydrocarbon correctly as CO2 and H2O
but surprisingly close to half the number could not balance the no. of moles of O2.
For (ii), many students could recognise that the volume of CO2(g) produced is 60 cm3. However,
many failed to compare it to the volume of CxHy(g) and subsequently use this volume ratio to
determine the mole ratio of CxHy (g) : CO2(g)*.
Many students could have better managed the question by abstracting the information that the
initial volume is larger than the final by 60 cm3. And the gases present initially are CxHy,
O2(reacted) and O2(unreacted), while gases contributing to the final volume are CO2 and
O2(unreacted).

*volume ratio = mole ratio only applies to gases measured at the same temperature and pressure
conditions
E.g. When the volumes of 2 gases are 60 cm3 and 30 cm3 (1:2) at r.t.p, the mole of the 2 gases
would be (60/24) = 2.5 mol and (30/24)= 1.25 mol respectively (also in 1:2 ratio) as the molar
volume (at r.t.p) is 24 dm3/ mol.

(d) (i) CH2=CH2 + 2H2O CH2(OH)CH2(OH) + 2H+ + 2e– [1]

MnO4– + 8H+ + 5e– Mn2+ + 4H2O


–––––––––––––––––––––––––––––––––––––––––––––––––––––––––
5CH2=CH2 + 2H2O + 2MnO4– + 6H+ 5CH2(OH)CH2(OH) + 2Mn2+ [1]

(ii) 5 .6
n(ethene) in 5.6 cm3 =
22.4
= 0.25 mol

Since mole ratio of CH2=CH2 : MnO4– is 5 : 2,

2
n(KMnO4) required = x 0.25 mol
5
[1]
= 0.1 mol

0 .1
volume of KMnO4 required =
0.05 [1]
= 2 dm3

©2016AndersonJC/CHEM 2
Comments:
For (i), many students did not read the question closely enough to recognise CH2(OH)CH2(OH) as
the product of oxidation of CH2=CH2. Correctly balancing the charges with electrons is still a
problem among many students.
For (ii), many students mistakenly used 24 dm3 mol–1 or 22.7 dm3 mol–1 (not sure from where) as
the molar volume at s.t.p. Students are reminded to refer to the Data Booklet (DB) for the correct
value and align other resources to the relevant values as given in the DB. The bigger problem for
this question, however, is to take the moles of KMnO4 and multiply it by the molar volume to find
the volume of KMnO4. Do you know what the problem is here?

(e) CO2 has a simple molecular structure in which the CO2 molecules are held together by [3]
weak instantaneous dipole–induced dipole interactions / intermolecular forces.

SiO2 has a giant molecular structure. It has a much higher boiling point as more
energy is required to break the strong, extensive covalent bonds between the Si and
O atoms.

[1]: correct structure of, and bonding in, each oxides


[1]: compared strength of these interaction and link to the energy needed to break
them

Comments:
It was very encouraging to see many scripts with good structure of answers. (i.e. state structure of
each oxide and their bonding; and finally compare in terms of energy required to justify the
difference in melting point). Keep it up!
Some students, however, could not identify the structure and bonding of SiO2 correctly and / or
give incorrect description such as Si and ‘O2’ atoms are held strongly, electrostatic forces between
SiO2 molecules etc.
A more serious misconception was to think that the weak intermolecular forces of attraction of CO2
are between the ‘covalent bonds of carbon and oxygen atoms’.

©2016AndersonJC/CHEM 3
2 (a) (i) heat evolved or absorbed when 1 mole of compound is formed from its [1]
constituent elements in their standard states under standard conditions.

(ii) Value of a: 0 [1]

H2(g) is the standard state of hydrogen and hence no heat is exchanged.

Comments:
Good effort shown in memorising definitions. Students who were not given credit mostly left out
the mention of standard state. A large number of students even thought that standard states (solid,
liquid or gas) is the same as standard conditions (298 K, 1 atm).

(b) (i) Horeaction 2 = 2Hof (SO2) + 2Hof (H2O) + 2Hof (O2) – 2Hof (H2SO4) [1]
2Hof (H2SO4) = 2(–297) + 2(–242) + 2(0) – (+439)
Hof (H2SO4) = –758.5 kJ mol–1

(ii) Horeaction 1 = [Hof (H2SO4) + 2Hof (HI)] – [Hof (I2) + Hof (SO2) + 2Hof (H2O)] [1]
= (–758.5) + 2(26.5) – [(62.4) + (–297) + 2(–242)]
= +13.1 kJ mol–1

(iii) Horeaction 3 = Hof (H2) + Hof (I2) – 2Hof (HI) [1]


= 0 + 62.4 – 2(26.5)
= +9.4 kJ mol–1

Comments:
For (i), a common mistake was to overlook the coefficient 2 for Hof (H2SO4) in the computation.
As expected, some included the BE(O=O) in the calculation while applying the general equation
Horeaction 2 = ∑Hof (product) – ∑Hof (reactant). Students must note that Hof (O=O) is not the same
as BE(O=O) as they involve totally different enthalpy changes! A significant number of students
did not include the ‘+’ sign for positive enthalpy changes.

(c) (i) [3]


Energy uncatalysed

Ea,b = 173.6 kJ mol–1


Ea,f = 183 kJ mol–1 Ea,b’ = 85 kJ mol–1
H2(g) + I2(g)
2HI(g) H = +9.4 kJ mol–1
catalysed

progress of reaction

[1]: correct labeling of axes and energy profile (activation energy shown as
between reactant and the transition state)
[1]: H arrow pointing from reactant to product energy level
[1]: correct Ea,b (Ea for backward reaction) calculated (ecf)

(ii) activation energy for the forward reaction = 85 + 9.4 = 94.4 kJ mol–1 [2]

[1]: energy profile with lower energy level transition state and Ea,b’ correctly
labelled
[1] correct Ea’ (forward reaction) calculated

©2016AndersonJC/CHEM 4
Comments:
 The x–axis should be labelled ‘progress of reaction’ or ‘reaction pathway’, not ‘time’! The curve
indicates the energy level at each stage of the reaction, not necessarily the energy level at a
specific time.
 Arrows for H and activation energy should be one–directional (not doubled–headed arrows).
 Note that the 2 energy profiles (catalysed and uncatalysed) must be labelled clearly. Relevant
values should also be included, e.g. the activation energies of the backward reaction.

©2016AndersonJC/CHEM 5
3 (a) (i) heat absorbed / required to remove 1 mole of electrons from 1 mole of singly– [1]
charged, gaseous cation to form 1 mole of doubly–charged gaseous cation.

(ii) C is Be; 1s2 2s2 [1]

(iii) (I)
From B+ to C+, nuclear charge increases but there is an additional (inner filled) [1]
quantum shell.
Valence electron is further away from nucleus, resulting in a weaker electrostatic [1]
attraction between the valence electron and the nucleus.

(II)
2nd IE generally increases from elements C to I. Nuclear charge increases. [1]
Shielding / screening effect remains relatively constant due to same number of [1]
quantum shells. Effective nuclear charge increases resulting in a stronger
electrostatic attraction between valence electron and nucleus.

(III)
There is inter–electronic repulsion between the paired 2p electrons in H+ as [1]
compared to G+, resulting in greater ease of removal of the electron.

Comments:
Students need to be careful of the terms used when defining the second I.E., and not to confuse
terms such as ‘cations’, ‘atoms’ and ‘electrons’. About half the cohort correctly deduced that
element C has one valence electron left after an electron had been removed, and hence belongs
to Group 2. Some suggested a Group 2 element from Period 3, ignoring the information (Period 2)
given in the question.
To do well in part (iii), students need to be familiar with the 2 trends in syllabus (down Group and
across Period) and the 2 anomalies across Period 2. Those who picked out the correct trend need
to be careful in giving all key points in their answers in order to gain the full credit.

(b) (i) H1: 1st and 2nd ionisation energy of Sr(g) [1]

H2: bond energy of Cl–Cl (accept 2 x Hat) [1]

(ii) By Hess’ Law, [1]


164 + 244 + 548 + 1060 + 2(–349) + LE = –829
LE = (−829) – [164 + 244 + 548 + 1060 + 2(–349)] [1]
= –2147 kJ mol−1

[1]: substitution of relevant values from question and from Data Booklet
(abstracting)
[1]: final answer with correct units

(iii) q q-
L.E. α
r  r
q+, q– and r– are the same but [1]
Mg2+ has a smaller cationic radius than Sr2+, (shorter inter–ionic distance)
Hence, stronger electrostatic forces of attraction between Mg2+ and Cl– as [1]
compared to SrCl2, therefore lattice energy of MgCl2 is more exothermic than
SrCl2.

©2016AndersonJC/CHEM 6
Comments:
To recognise H1, H2 and H3, students must be familiar with the various enthalpy changes
definitions.
For calculation in (ii), students must also know how to extract relevant data (out of the various
data) from the Data Booklet. A handful were still very careless with the ‘+’ and ‘–’ in their working.
For part (iii), students need to recall the factors affecting lattice energy. Note that ‘stronger
electrostatic forces of attraction leading to more energy absorbed to break the attraction’ is wrong,
because lattice energy is defined as energy released when attractions are formed.

©2016AndersonJC/CHEM 7
4 (a) (i) [CO ][H 2 ] 3 [1]
Kc =
[CH 4 ][H 2 O]

(ii) CH4(g) + H2O(g) CO(g) + 3H2(g) [4]


initial amt. / mol 1 5
change in amt / mol –0.95 –0.95 +0.95 +3(0.95)
amt. at eqm / mol 0.05 4.05 0.95 2.85
conc. at eqm / 0.05 4.05 0.95 2.85
mol dm–3 2 2 2 2

[CO ][H 2 ] 3
Kc =
[CH 4 ][H 2 O]
(0.475 ) (1.425 ) 3
=
(0.025 ) (2.025 )
= 27.2 mol2 dm–6

[1]: equilibrium concentrations


[1]: correct concentration change for CH4
[1]: Kc value (ecf)
[1]: units

Comments:
Most students could write the correct Kc expression. Those who used the ICE table could better
work out the equilibrium concentrations of the various compounds, though there were still a
handful who did not multiply the change in the number of moles of H2 by a factor of 3. Students
must note that the change in the number of moles of the compounds follows the mole ratio in the
balanced equation.

(b) (i) Le Chatelier’s Principle states that if a change is made to a reversible reaction in [1]
dynamic equilibrium, the position of equilibrium shifts so as to minimise that
change and to re–establish equilibrium.

(ii) When volume of the reactor increases, pressure of the equilibrium mixture [2]
decreases. Hence, position of equilibrium (P.O.E.) shifts to the right to increase
the number of moles of gaseous molecules and pressure.
OR
When volume of the reactor increases, concentrations of all the compounds
decreases. The ratio of the concentrations of the products over the reactants is
lower than at equilibrium. Hence, position of equilibrium (P.O.E.) shifts to the
right to increase the concentrations of the products.

[1]: effect of V increase


[1]: effect on P.O.E.

When temperature increases, the forward endothermic reaction is favoured. [2]


Hence, P.O.E. shifts to the right to decrease the temperature.

[1]: effect of T increase


[1]: effect on P.O.E.

©2016AndersonJC/CHEM 8
Comments:
Most students could define Le Chatelier’s Principle as well as how the P.O.E. would shift when the
volume and temperature changed. However, there were a few students who discussed the
increase in volume of the reactor in terms of a decrease in the concentrations of all the
compounds but could not correctly explain the effect on position of equilibrium after that.

(c) (i) heterogeneous catalysis [1]

(ii) electron from C atom [1]


C O
electron from O atom

(iii) H = [BECO + 2BEO–H] – [2BEC=O + BEH–H] [2]


–41 = BE(CO) + 2(460) – [2(740) + 436]
BECO = 955 kJ mol–1

[1]: correctly quote all BE


[1]: final answer (ecf)

Comments:
Many students did not attempt this part. For part (ii), many students drew diagrams where a
double bond is formed between carbon and oxygen atoms, and did not realise that in doing so,
carbon did not have an octet configuration.
Given that both carbon and oxygen are in Period 2 and cannot accommodate more than 8
electrons in their valence shell, the oxygen atom donates two of its electrons to form a dative bond
to carbon, in addition to the double bond to achieve octet configuration. Students are reminded not
to use circles to represent orbitals when drawing dot and cross diagram.
Part (iii) required students to estimate a value for the bond energy of CO, which some students
misinterpreted to mean that no calculations were required. Students need to realise that the bond
energies used in the calculation are all average values, hence the calculated bond energy of CO is
just an estimation.

©2016AndersonJC/CHEM 9
5 (a) (i) VS O 2  [1]
1 2 3
Rate α (or )
time t

rate of reaction is inversely proportional to the time taken for the colour of
bromine to disappear (and directly proportional to the volume of S2O32– used)

[1]: in words or expression

(ii) Expt no. Time relative initial rate / s–1 [4]


1 33 0.0303
2 100 0.0100
3 67 0.0149
4 50 0.0200

Since the total volume is kept constant (at 100 cm3), volume of reagent is directly
proportional to concentration.

Comparing expt. 2 and 3,


15 0.0149
When [KI] increases by = 1.5 times, initial rate increases by = 1.5
10 0.01
times
 order of reaction with respect to KI is 1

Comparing expt. 2 and 4,


15 0.02
When [H2O2] increases by = 2 times, initial rate increases by = 2 times
10 0.01
 order of reaction with respect to H2O2 is 1

Using expt. 1 and 2,


rate1 k [H 2 O 2 ]1 [KI]1 [HCl ]1n

rate 2 k [H 2 O 2 ] 2 [KI] 2 [HCl ] n2
0.0303 (15)(10)(5) n

0.01 (5)(10)(10) n
 (½)n = 1.01
n=0
Order of reaction with respect to HCl is 0

[1]: initial rates for all 4 expts


[1]: order of reaction wrt each reactants

(iii) Rate = k [H2O2] [KI] [1]

Comments:
Mention of an inverse or reciprocal relationship was needed for (i).
For (ii), quite a handful did not answer the question based on requirements by the question –
CALCULATE the initial rate for each of the 4 experiments and then USE the results to deduce. As
a result, conclusions made were often random and vague because there was no clear evidence
which sets of data were used for comparison. Students are encouraged to state clearly in their
deduction when answering such questions in future.
The usual errors of leaving out rate constant k from the rate equation and stating k [H2O2] [KI] as
the rate equation were still common in (iii).

©2016AndersonJC/CHEM 10
(b) (i) (refer to the plotted graph) [4]

time taken for [H2O2] to decrease from 0.0200 to 0.0100 mol dm–3
= 325 s

time taken for [H2O2] to decrease from 0.0100 to 0.0050 mol dm–3
= 645 – 325
= 320 s

Since the two t½ values are relatively constant, order of reaction w.r.t. H2O2 is 1

[1]: for correct scale and axes used


[1]: all points are correctly plotted
[1]: determination of half−life with construction lines (clearly shown) and t½ is
constant ( 1 small square – i.e. 10 s for the graph plotted)
[1]: order of reaction w.r.t. H2O2

gradient of tangent at 0 s = (0.0200  0.0100 ) [1]


(0  225 )
= –4.44 x 10–5 mol dm–3 s–1

initial rate = 4.44 x 10–5 mol dm–3 s–1 (accept: 2.44 x 10–5 to 6.44 x 10–5)

(ii) When initial [H+] increases from 0.300 mol dm–3 to 0.400 mol dm–3 while [H2O2] [2]
5
and [I–] are kept constant, the initial rate remains constant ( 4.2x105 = 1).
4.2x10
Hence, order of reaction with respect to H+ is 0.

When initial [I–] increases 2 times from 0.100 mol dm–3 to 0.200 mol dm–3 while
[H2O2] is kept constant (and order of reaction wrt H+ is zero), the initial rate also
5
increases ( 4.2x10 5 ) = 2 times. Hence, order of reaction with respect to I– is 1.
2.1x10

Alternatively
You can use the initial rate calculated in (i) to make the conclusion though it
would be good to use the data given in the table in case your initial rate
calculated in (i) is not correct or deviates too much from expected as you can
see from the above allowed range.

[1] each correct order of reaction

(iii) rate = k [H2O2] [I–] [3]


4.2 x 10–5 = k (0.0200) (0.200)
k = 0.0105 mol–1 dm3 s–1

[1]: rate equation (including rate constant k)


[1]: value of k
[1]: units for k

©2016AndersonJC/CHEM 11
(iv) [4]
Number of Represents no. of molecules with energy
greater or equal to Ea (T1)
molecules T1
with energy
T2 > T1
Represents no. of molecules with
energy greater or equal to Ea (T2)
T2

Energy

Ea

When temperature increases, the (average) kinetic energies of the reactant


molecules increase.
As shown on the diagram, the number of reactant molecules with energy greater
or equal to the activation energy will increase.
This results in an increase in the frequency of effective collisions. Hence, the
rate of reaction increases.

[1]: correct axes, shape of graph (including beginning from origin)


[1]: correct shift of graph and shading when T increase
[1]: correct explanation (in terms of ave KE increase and frequency of effective
collision increase)
[1]: correct conclusion

Comments:
A commendable effort by some although a significant number wrongly plotted the point (315,
0.0103) and hence lost a mark for (i). Students are reminded to present their reasoning for the
deduction of order of reaction clearly:
 determination of at least 2 half–life with clear construction lines on the graph paper and
 using 2 or 3 (relatively) constant half–life to conclude the order of reaction on the writing paper.

For (ii), the most unambiguous way of presenting the relationship would be to use the
mathematical representation given in the answer.

Besides the same error mentioned for (a)(iii), it was evident that most students had forgotten
about the order of reaction wrt H2O2, which they had deduced in (i), when stating the rate equation
for the reaction in (iii).

Most students were able to reproduce the required answers for (iv) in a clear manner. However,
some have to be mindful in labelling clearly the axes of the graph and to indicate clearly which of
the two graphs drawn is at a higher temperature. Other common errors were to start the graph
above the point of origin and to omit the fact that at a higher temperature, the average kinetic
energy of the molecules increases. The link between the effective collisions and rate of reaction
must also be clearly established in the explanation (i.e. frequency or no. per unit time). Stating that
the chances of effective collisions increase or there are more effective collisions were insufficient.

©2016AndersonJC/CHEM 12

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