CChO Local 2012 Solutions

Chinese Chemistry Olympiad

2012

3 Hours

Question 1 2 3 4 5 6 7 8 9 10 11 Total

Points 7 7 10 5 8 7 10 16 12 6 12 100
 CChO Local 2012 Solutions

Problem 1 [7%]
1-1 Aqueous ammonia of appropriate concentration is added dropwise to the aqueous solution of
zinc sulfate to an excess, and two main reactions occur. Briefly describe the experimental
phenomena and write the ion equation for the two-step main reaction.

The solution will first exhibit a white gelatinous precipitate of Zn(OH)2 followed by
redissolution due to complexation to form Zn(NH3)42+
1) Zn2+ + 2NH3 + 2H2O → Zn(OH)2(s) + 2NH4+
2) Zn(OH)2 + 2NH4+ + 2NH3 → [Zn(NH3)42+](aq) + 2H2O

1-2 The compound [Cu(pydc)(amp)]·3H2O has formula C11H14CuN4O7 (pydc and amp are
organic ligands containing aromatic rings). Thermogravimetric analysis shows that the
compound thermally decomposes in two steps. The first weight loss peak accounts for a weight
loss of approximately 15%. The second decomposition occurs between 400 and 500 ºC leaving
behind a solid residue with a mass of 21% of the original compound mass. Determine the
following:
Relevant Paper:
https://www.researchgate.net/publication/221765752_Supramolecular_assembled_of_hexameric
_water_clusters_into_a_1D_chain_containing_H2O6_and_H2O4O2_stabilized_by_hydrogen_b
onding_in_a_copper_complex

(1) What causes the weight loss occurring during the first step?

The answer is likely loss of H2O. MW(C11H14CuN4O7) = 377.55 g/mol.

0.15·377.55 = 56.63 which is in the realm of experimental error for 3·18 = 54 g/mol

Indeed, 3·18/377.55 = 14.3% ≈ 15%

(2) What is the solid residue remaining after further heating to 500ºC? Justify your answer.

377.55·0.21 = 79.29 g/mol which is close to MW(CuO) = 79.55 g/mol (within experimental
error)

Thus the solid residue is CuO. Note that the original question listed a mass % of 20.0 which
was the actual figure reported in the paper. This leads to a molar mass of 75.51 g/mol. As a
result the official answer says something like a mixture of CuO and Cu2O, but at high
temperature equilibrium I find this answer unlikely, so I modified the numbers.
 CChO Local 2012 Solutions

Problem 2 [7%]
A and X are two common non-metallic elements. The sum of their atomic numbers is 22, and the
sum of their valence layer electron counts is 10. Under certain conditions, AX, AX3 (a common
Lewis acid), A2X4 and A4X4 can be generated.
A(s) + 3/2 X2(g) → AX3(g)

After being passed through a mercury electrical discharge, the following reactions can follow
AX3(g) → AX(g) + 2X(g)
2Hg + 2X(g) → Hg2X2(g)
AX(g) + AX3(g) → A2X4(g)
4AX(g) → A4X4(s)

2-1 Determine the identities of A and X

A:B X:Cl

2-2 A4X4 has 4 three-fold rotation axes, and there are 4 atoms around each A atom. Draw the
structural formula of A4X4

2-3 Write the equation for the reaction of AX3 with CH3MgBr in a 1:3 molar ratio.

All acceptable:
BCl3 + 3CH3MgBr → B(CH3)3 + 3 MgBrCl
AX3 + 3CH3MgBr → A(CH3)3 + 3 MgBrX
BCl3 + 3CH3MgBr → B(CH3)3 + 3/2 MgBr2 + 3/2 MgCl2

2-4 Write the equation for the alcoholysis of A2X4 by ethanol.

All acceptable:
B2Cl4 + 4 C2H5OH → B2(OC2H5)4 + 4HCl
A2X4 + 4 C2H5OH → A2(OC2H5)4 + 4HX
 CChO Local 2012 Solutions

Problem 3 [10%]
Aqueous solutions of CuSO4 can react with K2C2O4 to form a blue crystal of unknown
composition. The formula of the crystal was determined by the following experiments
(a) Weigh 0.2073 g of the sample, put it into an Erlenmeyer flask, add 40 mL of 2 mol L-1
H2SO4, and dissolve the sample with slight heat. Add 30 mL of water, heat to near boiling, titrate
with 0.02054 mol L-1 KMnO4 solution to the end. This step requires 24.18 mL of titrant.
(b) Next, the solution is sufficiently heated until the color changes from lavender to blue. After
cooling, 2g of KI solid and an appropriate amount of Na2CO3 were added. The solution turned
brown and a precipitate was formed. The solution was titrated with 0.04826 mol L-1 Na2S2O3
solution, with starch indicator added near the end point, to the end point, consuming 12.69 mL.

3-1 Write the equation for the titration reaction occurring in step (a).
2MnO4- + 4 H2C2O4 + 6H+ → 2Mn2+ + 10 CO2 (g) + 8H2O *

3-2 Write the equation for the reaction causing the color change from lavender to blue in step (b).
4MnO4- + 12H+ → Mn2+ + 5O2 (g) + 6H2O

3-3 Write the reaction occurring upon addition of KI in step (b). Also write the equation for the
Na2S2O3 titration reaction.
KI reacts with Cu2+ to form a white precipitate of CuI and a brown solution of I3-
2Cu2+ + 5 I- → 2CuI (s) + I3-

3-4 Determine the chemical formula of the blue crystal by calculation (all coefficients in the
formula are integers)
n(C2O42-) = 0.02054 M·24.18 ml·5/2 = 1.241 mmol
n(Cu2+) = 0.04826 M·12.69 ml = 0.6124 mmol
n(C2O42-) ≈ 2 n(Cu2+) → Solid contains [Cu(C2O4)22-]
Between Cu2+ and K+ for the counterion, K+ is more likely (although you can test both).
So the crystal has the formula K2Cu(C2O4)· xH2O
If we try using the formula:
n(H2O) · 18 g/mol = 0.2073 - n(Cu2+)·MW(K2Cu(C2O4)2)
n(H2O) · 18 g/mol = 0.2073 - 0.5·n(C2O42-)·MW(K2Cu(C2O4)2)
We get x = n(H2O)/n(Cu2+) = 1.15 and 0.989 respectively, which tells us that the complex is a
monohydrate.

K2Cu(C2O4)2·H2O
 CChO Local 2012 Solutions

Problem 4 [5%]
Neutron diffraction experiments carried out in 1967 determined that there are only three ions in
the crystal structure of trans-[Co(en)2Cl2]Cl·HCl·2H2O: X+, Cobalt-containing A+ and Cl-. All
atoms in X+ are coplanar. X+ also has a center of symmetry and three mirror planes that are
perpendicular to each other. Note: en is an abbreviation for ethylenediamine.
Relevant Paper:
https://www.sciencedirect.com/science/article/abs/pii/0020165067800862?via%3Dihub

4-1 Draw the structural formula of the stereoisomers of A+ and its stereoisomers
A+: Stereoisomers

4-2 Draw the structural formula of X+.

X+ = H5O2+ (very technically this is not planar, but oh well)
 CChO Local 2012 Solutions

Problem 5 [8%]
A supramolecular crystal is obtained by mixing aqueous solutions of urea and oxalic acid. X-ray
diffraction experiments showed that the crystal belongs to the monoclinic system, with unit cell
parameters a = 505.8 pm, b = 1240 pm, c = 696.4 pm, β = 98.13°. The crystal’s supramolecular
structure is caused by hydrogen bonding between adjacent molecules leading to a
two-dimensional lattice. The crystal has density D = 1.614 g·cm-3.

5-1 Determine the ratio of oxalic acid molecules to urea molecules present in the crystal.
V = abc sin(β) = 4.32·108pm
D = MW(formula unit)/V → MW(formula unit) = 420.25 g.mol

MW(H2C2O4) = 90 g/mol, MW(OC(NH2)2) = 60 g/mol

From guess and check we get 4·60 + 2·90 = 420 g/mol

Thus the ratio of oxalic acid molecules to urea molecules is 1: 2

5-2 Using structural formulas draw the hydrogen bonding in a formula unit of the crystal
 CChO Local 2012 Solutions

Problem 6 [7%]
2,3-pyridinedicarboxylic acid, commonly known as quinolinic acid, is a central neurotoxin
related to Alzheimers and Parkinsons. At room temperature, quinolinic acid exists as a solid, and
upon heating at 185-190 ºC, CO2 is released forming niacin.

6-1 In the solid state, quinolinic acid adopts its lowest energy configuration. Draw this
configuration (you do not need to draw lone pairs or irrelevant hydrogen atoms).

6-2 the pKa1 of quinolinic acid in aqueous solution is 2.41, write the equation for its first
ionization (draw organic molecules as structural formulas).

6-3 Draw the structure of niacin.

 CChO Local 2012 Solutions

Problem 7 [10%]
In aqueous solutions of boric acid with a total boron concentration of ≥ 0.4 mol L-1, ions like
tetraborate (B4O5(OH)42-), pentaborate (which has charge –1), and two distinct kinds of triborate
ions with charges -1 and -2 can form. These polyborate ions are formed by condensation of
B(OH)3 and B(OH)4-. The boron atoms in the structure are connected to form a ring by oxygens
in a B-O-B fashion.
Source Paper:
https://onlinelibrary.wiley.com/doi/10.1002/0471238961.0215181519130920.a01.pub2
7-1 In the above pentaborate ions, the chemical environment of all three coordinated boron
atoms is exactly the same. Draw the structural formula for pentaborate (you do not need to draw
lone pairs)

7-2 The figure on the right shows the

relationship between the existence form and
pH of the boric acid-borate system when the
total concentration of boron is 0.4 mol L-1.
The numbered areas (labeled 1,2,3,4) between
the curves represent the fractional
composition of the 4 kinds of polyborate ions
at each pH. Determine the chemical formulas
of the polyborate ions 1-4.

1: B5O6(OH)4- 2: B3O3(OH)4-

3: B4O5(OH)42- 4: B3O3(OH)52-
 CChO Local 2012 Solutions

Problem 8 [16%]
The pourbaix diagram on the right shows the
relationship between the most stable species of
uranium over a range of cell potentials and pH in a
the carbonic acid-carbonate system (total carbonate
concentration 1.0 × 10-2 mol L-1) using the standard
hydrogen electrode as the reference value.

For comparison, the dashed lines show the E-pH

relationship for H+/H2 and O2/H2O pairs.

8-1 Calculate the concentrations of the main species in a carbonic acid-carbonate system at pH of
4.0 and 6.0 respectively
H2CO3: Ka1 = 4.5·10-7 , Ka2 = 4.7·10-11

Note that this first part has nothing to do with Uranium (it's just about the bicarbonate system)
Ctot = 1.0 ·10-2 M = [H2CO3] + [HCO3-] + [CO32-]

[HCO3-] = Ka1 ·[H2CO3]/[H+], [CO32-] = Ka1Ka2 [H2CO3]/[H+]2

At both pH values H2CO3 dominates.

At pH = 4, it is safe to assume [H2CO3] ≈ 1.0 ·10-2 M

It follows that [HCO3-] = 4.5·10-5 M, [CO32-] = 2.115·10-9 M

At pH = 6, [HCO3-] and [H2CO3] are the primary species, [CO32-] is comparatively negligible.

[HCO3-]/[H2CO3] = Ka1/[H+] = 0.45 , so Ctot = 1.45 [H2CO3], so [H2CO3] = 6.90·10-3 M

It follows that [HCO3-] =3.10·10-3 M, [CO32-] = 1.46·10-7 M

8-2 In the figure, a and b are two straight lines with pH = 4.4 and 6.1, respectively. Write the
equations for the transformation of uranium species corresponding to a and b, respectively.

Recall that H2CO3 is the primary species at these pH values

a: UO22+ + H2CO3 → UO2CO3 + 2H+

b: UO2CO3 + H2CO3 → UO2(CO3)22- + 2H+

 CChO Local 2012 Solutions

8-3 Write the half cell potential equations for the reactions corresponding to the straight lines c
and d, respectively, and explain the reason for the positive or negative slope.
The reaction for line c is
4UO2+ + H2O + 2e- → U4O9 + 2H+
The reaction for line d is
U4O9 + 2H+ + 2e- → 4UO2 + H2O
The equations for the lines comes from the nernst equation for each half reaction. Above this
potential, the oxidation is spontaneous, while below it, the reverse reaction (reduction) is
spontaneous.

If all non H+ species are at standard concentrations then the half

E = Eº – 0.0592/n log([H+]m) = Eº + m/n · 0.0592pH

c: E = Eº – 0.0592/2 log ([H+]2) = Eº + 0.0592 pH

The slope is positive because [H+] is a product.

d: E = Eº – 0.0592/2 log([H+]–2) = Eº – 0.0592 pH

The slope is negative because [H+] is a reactant.

8-4 Write the reaction that occurs upon adding UCl3 to a solution buffered at pH = 4.0

2UCl3 + 4H2O → 2UO2 + 6H+ + 6Cl– + H2

8-5 Can UO2(CO3)34- and U4O9(s) coexist between pH = 8-12? Can UO2(CO3)34- and UO2(s)
coexist? Justify your answers.

UO2(CO3)34- and U4O9(s) can coexist between these pH values because their stability regions
share a boundary (along which the two species can coexist).
UO2(CO3)34- and UO2(s) cannot coexist for the same reason.
 CChO Local 2012 Solutions

Problem 9 [12%]
The Knoevenagel reaction is a useful type of condensation reaction. As shown in the figure
below, diethyl malonate and benzaldehyde react in the presence of piperidine to form diethyl
2-benzylidenemalonate.

9-1 Draw the nucleophile in the reaction. 9-2 Briefly describe the role of piperidine
Piperidine is a base catalyst for the
aldol/Knoevenagel condensation. It can also
form an iminium ion with benzaldehyde
rendering it more electrophilic.

9-3 Compound A is a precursor to the anticonvulsant drug gabapentin D. Propose a synthesis of

A using 2 organic reagents.
Cyclohexanone + Malonic Acid

Gabapentin (D) is synthesized as follows:

9-4 Draw the structural formulas of B, C and D in the above scheme.

B C D
 CChO Local 2012 Solutions

Problem 10 [6%]
The taste of pepper is mainly derived from capsaicinoids. The synthetic route of capsaicin F is
shown below:

Draw the structural formulas of compounds A-F.

A B

C D

E F
 CChO Local 2012 Solutions

Problem 11 [12%]
11-1 The oxymercuration-demercuration reaction of alkenes is similar to alkene bromination.

The main product formed when 4-penten-1-ol is reacted under the same conditions is B. Draw
the structural formulas of A and B.

A B

11-2 Which of the following organic compounds are aromatic?

2 and 5

Compound A reacts in the following two steps to give compound D. Answer the following
questions:
 CChO Local 2012 Solutions

11-3 Write the formula for compound B

O3

11-4 Circle the oxygen atom in C that came from A

11-5 Draw the structural formula of compound D.

D forms from an intermediate which undergoes an aldol condensation