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
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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.

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:

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

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

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.

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

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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).

3-2 Write the equation for the reaction causing the color change from lavender to blue in step (b).

3-3 Write the reaction occurring upon addition of KI in step (b). Also write the equation for the
Na2S2O3 titration reaction.

3-4 Determine the chemical formula of the blue crystal by calculation (all coefficients in the
formula are integers)
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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.

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

4-2 Draw the structural formula of X+.

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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.

5-2 Using structural formulas draw the hydrogen bonding in a formula unit of the crystal
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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.

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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.

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: 2:

3: 4:
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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 aqueous 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

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.

a:

b:
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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.

c:

d:

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

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.
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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

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

A using 2 organic reagents.

Gabapentin (D) is synthesized as follows:

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

B C D
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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
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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?

Compound A reacts in the following two steps to give compound D. Answer the following
questions:
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11-3 Write the formula for compound B

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

11-5 Draw the structural formula of compound D.