Report and Analysis to the

Malaysian IChO Team Selection Quiz 2014

Third Phase
Prepared by:

Yau Ching Koon

Answers were accessed using points that were deemed suitable by the author and may not reect the true marks given. Generally, marks will not be awarded heavily to pure memory work but rather to the science and thinking skills displayed unless the nature of the answer required is so. Special thanks to Goh Jun Yan for his marking the papers and aiding in the arbitration process.

Version 2

Suggested answer and analysis

Question 1 (a) The standard potential of a cell is the potential difference of that cell in standard conditions (pressure P = 1 bar, temperature T = 298.15 K and activity, a = 1 for solutes in solution or fugacity, f = 1 for gases in gaseous mixture) with respect to the standard hydrogen electrode (SHE). [2]

1 point is given for potential difference w.r.t. standard hydrogen electrode and 1 point for mentioning that the cell is in standard condition.
Many students failed to answer this question correctly because they could not appreciate that an electric potential cannot be measured but can be measured as a difference, hence the term potential difference. Being a difference, another cell must be quoted naturally and in this case, the SHE. All students do not know that the new standard pressure recommended by IUPAC is 1 bar! (b) There are three modes of mass transfer: migration, diffusion and convection. Migration is the movement of a charged body under the inuence of external electric eld. Diffusion is the net movement of a chemical species due to a gradient in chemical potential or concentration. Convection can be classied into two: a natural convection due to density gradient and a forced convection due to stirring introduced to the bulk liquid. [7]

1 point each for identifying each modes of mass transfer. 1 point each for explaining migration and diffusion. 2 points for explaining convection. It is necessary to mention the cause of the mass transfer in the explanation to show that the students could distinguish them from one another.
Most students do not realize that the natural convection can be obtain as a result of density gradient. During the operation of a electrochemical cell, the electrolyte will be heated because of its own resistance and due to inhomogeneous heating and cooling, different parts of the electrolyte will attain different density. Density is dependent on temperature. Hence, the density gradient produces a natural convection. (c) If the electron transfer process is the rate determining step, then other contributions to the rate such as the rate of mass transfer and that of the preceding reactions are negligible. The rate of mass transfer can be kept at minimum by affecting an effective stirring while the rate of preceding reactions can be kept at minimum by choosing a suitable fast equilibrium system for investigation, e.g. aqueous sulfuric acid in which the dissociation occurs rapidly. Under such conditions, the rate of reaction is the rate of electron transfer at the equilibrium potential, Eeq . The overpotential, = E Eeq , is related to the electric current, i in such condition according to the Tafel equation = a + b log i, where a and b are two empirical constants. The Butler-Volmer model was developed to explain the empirical Tafel equation, and the corresponding equation is given by C (0, t) C (0, t) i = O e F / RT R e(1) F / RT , i0 CO CR where i0 is called the exchange current (obtained as a limiting value as 0). 2 [3]

 1 point for understanding the relation of rate determining electron transfer step to other effects that contributes to the overall rate. 1 point for giving examples on how the other rates can be kept at minimum. 1 point for producing Tafel or Butler-Volmer equation.
Most students fair poorly in this question showing that the students does not comprehend electrode kinetics and in particular, the relationship between Butler-Volmer equation and Tafel equation. (d) If the electron transfer is rapid, then mass transfer or preceding reactions could be the rate determining step. In either case, the concentration of the reactants near the electrode will deplete and the product will increase. If we consider a reduction process (O becoming R), then [O] will decrease and [R] increase until the both are regulated by the rate mass transfer or preceding reactions. The incorporation of mass transfer effect to Butler-Volmer equation gives i = i0 1 i il ,c e F / RT 1 i il ,a e(1) F / RT . [2]

1 point for understanding the relation of electron transfer being the fast step to other effects that contributes to the overall rate. 1 point for discussing the concentrations of oxidised and reduced species.
Most did not answer this question. (e) Regretfully, answers to this part will not be produced because it is deemed as too much of pure memory work to the extent that it may not worth any points by the authors standard.

Question 2 (a) dsp2 : square planar, d2 sp3 : octahedral, dsp3 : trigonal bipyramid or trigonal bipyramidal. [3]

1 point each for correct answer.

Most students could answer this question. Some do not recognize dsp2 as square planar and answered tetrahedral instead while some erroneously spelled trigonal bypyramid. (b) The ve d orbitals are shown below. According to the crystal eld theory, six ligands approached a metal ion from and along the + x, +y, +z, x, y, and z axes. All the ve d orbitals will be destabilise because the metal is introduced into an environment with ligands but the orbitals dz2 and dx2 y2 would experience further repulsion because these orbitals are in direct overlap with the incoming ligands which usually bears negative charge or a pair of electrons. The degenerate ve d orbitals split into two groups: the rst comprises of dz2 and dx2 y2 and the second comprises of dxy , dxz and dyz . The rst group is called the e g orbitals while the second is called t2g orbitals,. The symbols are assigned according to their irreducible representations of the D4h group. [8]

1 point each for the orbitals drawn, clearly showing the region occupied on or in between the axes. 1 point for destabilisation of all orbitals in crystal eld and 1 point for justifying the splitting of ve d orbitals into two groups. 1 point for describing e g as composed of dz2 and dx2 y2 while t2g as composed of dxy , dxz and dyz . The last 3 points can be collectively awarded on a meaningful sketch of the corresponding energy level diagram.

dz2

d x 2 y2

dyz

dxz

dxy

Most students do not realize that the presence of ligands destabilised all the ve d orbitals. Some did not draw the ve d orbitals as required and some who had drawn did not label the axes. Overall performance is good. (c) The spectrochemical series is a list of ligands arranged in either ascending or descending order of crystal eld splitting energy produced by ligands in their complexes. This series is usually established with UV-Vis spectrophotometry. In the ascending order, the spectrochemical series for the ligands given is Cl , H2 O, NH3 , CN Thus, the crystal eld splitting energy for a complex, say [CoCl6 ]3 is the smallest while the crystal eld splitting energy in the complex [Co(CN)6 ]3 is the largest. [3]

1 point for dening spectrochemical series, 1 point for giving the correct arrangement of the ligands given, 1 point for illustrating the meaning of spectrochemical series.
Several students did not answer this question, some gave the wrong order, many could not understand the meaning of spectrochemical series and many did not gave example for further discussion. (d) Nickel(II) ion has eight d electrons in its complexes and both tetraamminenickel(II) and tetracyanonickelate(II) ions are square planar. Due to Jahn-Tellar effect, the octahedral shape is tetragonally distorted causing the ligands along the z-axis to be far from the metal ion. Therefore orbitals pointing closer to the z-axis experience less repulsion and stabilise, with dz2 becomes a1g , dxz and dyz becomes e g , dxy becomes b2g and dx2 y2 becomes b1g . Ammonia, being 4

a weak eld ligand allows the b1g energy level to be occupied in [Ni(NH3 )4 ]2+ where the electronic conguration 4 2 1 1 eg a1 g b2g b1g , is assumed. On the other hand, cyanide ion is a strong eld ligand in [Ni(CN)4 ]2 and forces the b1g electron to pair up with the electron in b2g resulting in the electronic conguration: eg
4

a1 g

b2g

. [4]

Hence [Ni(NH3 )4 ]2+ is paramagnetic while [Ni(CN)4 ]2 is diamagnetic.

1 point for recognizing that the tetragonal distortion results in the splitting of the t2g and e g orbitals to e g , a1g , b2g and b1g orbitals. 1 point each for electronic conguration of [Ni(NH3 )4 ]2+ and [Ni(NH3 )4 ]2+ (may be given as energy level diagram). 1 point for drawing conclusion.
Many students either did not answer the question or gave irrelevant responses. Some, without Periodic Table provided to them, used the wrong number of d electrons. Only one student produced the correct answer.

Question 3 (a) From Arrhenius equation, we have ln k = ln A where T /K = / C + 273. k /mol1 L s1 7.8 10 14 18 24 / C 400 410 420 430 440 ln k /mol1 L s1 2.05 2.30 2.64 2.89 3.18 1/ ( T /K) 0.00149 0.00146 0.00144 0.00142 0.00140 Ea R 1 , T

From a graph of ln k/mol1 L s1 against 1/ ( T /K), the gradient m obtained is: m=

Ea R

K = 13 605 Ea = 113 kJ mol1 [7]

1 point for effort to prepare the table, 1 point for conversion to T in kelvin, 1 point for effort to prepare graph, 2 point maximum for correct graph (penalty applied for any error), 1 point for calculating gradient, 1 point for correct nal answer including units.
Most students could do this question. The common mistake is not to realize that the unit is kJ mol1 and some forgetting the factor 103 in their calculation. Penalties were awarded for not attempting to draw the line of best t, graphs utilizing less than half of the graph paper provided, and for not providing enough ticks that include the terminal points. (b) From Arrhenius equation, we have ln (0.079) = ln A 1 Ea , R 508 + 273 Ea 1 ln (0.24) = ln A . R 540 + 273

Subtracting the one from another gives ln 0.079 Ea = 0.24 R 1 1 781 813 , 1 1 781 813
1

0.079 Ea = (8.314) ln 0.24

= 183 kJ mol1 ,

while ln A = ln (0.079) + 1.83 105 1 = 25.6, 8.314 781 A = 1.37 1011 mol1 L s1 . [6]

To be dimensionally consistent, the unit of A is the same as that of k.

1 point each for constructing two equations by substitution to the Arrhenius equation, 1 point each to solve for Ea and A, and 1 point each for correct answer (including units).
Most students can answer this part, however most who answered did not realize that the question seek for two values, Ea and A and many did not calculate A. Some did not give the correct unit for Ea and only a handful gave the unit for A. (c) If the experiments were made in large concentrations of O2 or M, then k 1 [O2 ][ M] The derived rate law simplies to k 2 [ O2 ] .

2k k [O ]2 [ M ] [O ]2 d[O3 ] = 1 2 3 = kobs 3 , dt k 1 [O2 ][ M] [O2 ]

where kobs = 2k1 k2 /k 1 and is consistent with the empirical rate law. NOTE: No derived rate laws can be conrmed to be valid, only to be ruled out if the empirical data is not consistent with the derived rate law. [2]

1 point for proposing experiments conducted in large concentrations of O2 or M. 1 point to show that the derived rate law simplies to the observed rate law.
Some students could not answer the question by providing irrelevant responses. That may be due to an unclear nature of the question itself.

Question 4 (a) The energy, E = h = 6.63 1034 and 2.4 109 = 1.59 1027 kJ,

E=

2.4 109 = = 8 102 cm1 . c 3 1010 [4]

1 point each for correct substitution, 1 point each for correct answer including units.
Most students could answer this question. Common mistake are substituting the wrong value for c and not presenting E in the required unit. (b) Microwave. [1]

Many could answer this correctly. Some interesting answers encountered include IR, UV and radiowave. (c) A molecule will change its state of rotational motion upon absorbing a photon in the microwave region. [1]

 The word change of rotational state is necessary because the molecule may be in a rotational state already.
No student could answer this question correctly. For those who has selected microwave in part (b), many answered the molecule will rotate but that is insufcient because the molecule may already be rotating initially. Upon receiving a photon in the microwave region, the initial rotational state is excited to another rotational energy level. (d) Volume of the tank, V = 100 40 40 = 1.6 105 cm3 . Mass of water in the tank, m = 1 1.6 105 = 1.6 105 g. Amount of water molecules, n = 1.6 105 /18 = 8.9 103 mol. Number of water molecules, N = 8.9 103 6.023 1023 = 5.4 1027 . Number of water molecules to be excited, N = 10% 5.4 1027 = 5.4 1026 . Total energy required to excite the water molecules, E = 5.4 1026 1.59 1027 = 0.85 kJ. [6]

1 point each for each step.

Many could not solve the entire problem, perhaps because they do not understand the basic principles of quantum mechanics.

(e) The moment of inertia about the C2 axis, I = 2 1.0078 95.72 sin 104.5 2
2

= 1.155 104 u pm2 , = 1.917 1047 kg m2 .

[4]

1 point for attempt to calculate r, 1 point for attempt to calculate I , 1 point for the factor 2, 1 point for answer.
Most student could not understand the meaning of moment of inertia and most had used the reduced mass for the calculation which coincidentally gave the correct answer but no mark is awarded.

(f) The rst ve energy levels are F (0) F (1) F (2) F (3) F (4) where B=

= 0 (0 + 1) B = 0, = 1 (1 + 1) B = 2 B, = 2 (2 + 1) B = 6 B, = 3 (3 + 1) B = 12 B, = 4 (4 + 1) B = 20 B,

h 6.63 1034 = = 14.2 cm1 . 8 2 cI 8 2 3 1010 1.97 1047

[5]

1 point for calculating F, 1 point for drawing energy levels with increasing separation, 1 point for starting at J = 0, 1 point for labeling correctly, 1 point for calculating B.
Some students did not calculate the value of B, some did not start with J = 0 and some did not sketch the energy levels in increasing separation which is in clear violation to what one has calculated for F. (g) Infrared. Most students could answer this question. (h) The maximum number of vibrational normal modes that can be observed is 3 (3) 6 = 3. [2] [1]

1 point for calculation with 3 N 6, where N = 3 and 1 point for nal answer.
Most students could answer this question. (i) The possible vibrational normal mode for a water molecule are shown below (symmetric stretch, asymmetric stretch, bending).

[1]

1 point for providing at least one correct normal mode with clear indication of the type either by labeling or indicating with arrows.
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Most students could answer this question. = 3500 cm1 . We have = c (j) The vibrational mode of the OH bond is found typically at and since the frequency, is inversely proportional to the square root of reduced mass, under the assumption that the force constant for OH and OD bonds are similar, we have OH OD = OH = = OD OD OH 3500 OD = = 2555 cm1 . 1.37 1.77 = 1.37, 0.94

where OD = 2 16/18 = 1.77 u and OH = 1 16/17 = 0.94 u.

[8]

for OH bond, 1 point for knowing 1/ , 1 point 1 point for knowing a typical value of , 1 point each for calculating reduced mass for assuming k is constant, 1 point for knowing OD , 1 point for correct answer. of OH and OD, 1 point for calculating
Most students could not answer this question. Due to insufcient exposure to IR spectroscopy, and are not able to produce explicitly . they could not give a typical value of

Question 5 (a) There are two chair conformers of piperidine, C5 H11 N:

There are four chair conformers of 1,4-disubstituted piperidine including their isomers.

[8]

1 point each for the conformers drawn, 1 point for stating two chair conformers for piperidine, 1 point for stating four chair conformers for 1,4-disubstituted piperidine.
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Many students did not answer this question, perhaps because they could not recall the structure of piperidine. (b) The aromaticy of a compound is determined by four criteria, all of which must be satised: Compound (a) (b) (c) (d) (e) (f) (g) Aromatic? Y N Y N Y Y Y Cyclic? Y Y Y Y Y Y Y Planar? Y Y Y Y Y Y Y Fully conjugated? Y N Y Y Y Y Y Huckel rule? Y [2 = 4(0) + 2] N [4 = 4(?) + 2] Y [6 = 4(1) + 2] N [8 = 4(?) + 2] Y [6 = 4(1) + 2] Y [10 = 4(2) + 2] Y [14 = 4(3) + 2] [7]

1 point for each correct answer along with justication.

No student scored full marks for this question despite being simple, suggesting that the students are not explicitly exposed to the criteria for determining aromacity.

Question 6 (a) (a) three, (b) two. [2]

1 point for each correct answer.

All students are able to do this question. (b) (a) four, (b) three, (c) four, (d) four. [4]

1 point for each correct answer.

Structures (c) with 19 wrong responses, followed by (d) with 14 wrong responses and nally (a) with 11 wrong responses. O CH3 (c) (a) H3 C , (b) Br OCH3 . [2]

1 point for each correct answer.

Many students could solve the structure for (a) but only a handful could solve the structure for (b).

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Results
Since 20 marks are allocated on each question, the total points for each questions is weighed equally to compute the nal marks. Name James Loke Wen Liang Gan Kin Boon Leong Sheng Yuan Tan Ze Kai Khu Wai Hoong Ooi Kok Yong Ahmad Syahmi b. Adnan Marcus Lim Guozong Tow Boon Chee Denedy Wong Siong Yong Boon Zhen Hern Tan Yi Sheng Chen Yi Kit Lim Chun Wei Ooi Lim Seong Liang Chang Ji Shen Nur Amalina binti Azmi Mohamad Syahmi bin Mohd. Hothzani Eow Wei Siang Mohamad Ashiqeen b. Anwar Ali Tan Hooi Nee Wan Jia Wei Tong Cher Ling Institution Foon Yew High School INTI Foon Yew High School Sunway University College Kolej Matrikulasi Pahang Kolej Matrikulasi Pulau Pinang Kolej Mara Banting Kolej Matrikulasi Pulau Pinang Kolej Matrikulasi Pahang SMK Batu Lintang SMJK Jit Sin SMK Temerloh SMJK Jit Sin SMJK Heng Ee SMJK Chung Ling SMJK Chung Ling Kolej Matrikulasi Perak Kolej Mara Banting SMJK Heng Ee Kolej Matrikulasi Pulau Pinang SMK Tsung Wah Kuala Kangsar SMK Temerloh INTI Q1 7.4 8.4 7.7 9 8.7 10 7 6.7 7.7 7.7 9 7 7.7 8.7 7.4 7 6.7 8.7 4.7 4 4 8 6 Q2 16 13 17 8 10 9 16 9 9 10 8 10 5.5 6.7 5.5 8 4 4 7.7 7 0 10 9.5 Q3 14 12 9.7 13 14.7 8.7 11.7 13.7 14 15 12 13.4 11 10.7 13 10.7 10 12 8 8.7 12 4.7 0 Q4 21 17 22 20 17 17 11 10 12 5 17 14 16 15 9.7 6 11 5 11 10 13 4 4 Q5 5 5 0 5 3 4 0 0 3 2 0 0 0 2 2 0 0 0 0 1 0 0 0 Q6 6 5 6 5 5 7 6 8 5 6 5 5 6 4 4 4 5 4 5 4 4 3 6 Total 67.8 59.9 59.3 58.6 58.3 57.5 54.2 53.2 52.9 52.3 50.5 50.0 47.1 46.6 43.8 39.0 38.8 38.3 37.6 35.4 33.0 32.3 30.5

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