CHEMISTRY: ART, SCIENCE, FUN

THEORETICAL
EXAMINATIONANSWER SHEETSJULY 20, 2007
MOSCOW, RUSSIA
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Problem1

Name: _______________

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1.1.1 Structures:
Propanedial

1st isomer

2nd isomer

1.1.2 Circle the acidic hydrogen atom

HOOCCHCHH

The acidity of propanedial is caused bya) the stability of a carbanion due to conjugation with two carbonyl groupsb) weakness of C–H bond in a carbonyl groupc) hydrogen bonds between two propanedial molecules
The correct answer _______
1.2.1 The structures corresponding to minima on energy curve:

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Problem1

Name: _______________

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Student code: _________

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24.5

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1.3.1 The probability density(a) t = 0
Ψ 2 ( x, 0) =2

Ψ

-0,06

-0,04

-0,02

0,00

0,02

0,04

0,06

0,02

0,04

0,06Distance, nm(b) t = π/(2ω)

 π Ψ 2  x,= 2ω 2Ψ

-0,06-0,04-0,020,00

Distance, nm

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Problem1

Name: _______________

Quest. 1.1 1.2 2.1 3.1 3.2 3.3 3.4

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PointsStudent code: _________

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24.5

73

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4.5

246(c) t = π/ω πΨ 2  x,  =
 ω
2

Ψ

-0,06-0,04-0,020,00

0,02

0,040,06

Distance, nm

1.3.2

The probability of finding the proton in the left well = _______

1.3.3 The time of proton transfer
Your work:

t=The proton mean speedYour work:v=
1.3.4 The uncertainty of proton position∆x =Official English version.

Problem1

Name: _______________

Quest. 1.1 1.2 2.1 3.1 3.2 3.3 3.4

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Student code: _________

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24.5

73

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6The minimal uncertainty of proton velocityYour work:∆v =a) Proton is a rather heavy particle, and its tunneling in malonaldehyde can be described inclassical terms of position and velocityb) Proton tunneling is a purely quantum effect; it cannot be described in classical termsc) Uncertainty of proton velocity is so large that tunneling cannot be observed
experimentallyd) Uncertainty of proton velocity is so small that tunneling cannot be observed
experimentally
The correct answer is _______

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Problem
2

Name: _______________

Quest. 1.1 1.2 2.1 2.2 3.1 3.2 3.3 3.4 3.5

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228124215232

2.1.1 Thermodynamic data for the reaction (1):Your work:∆rG0 (1) =K=
2.1.2 Equilibrium constant for the reaction (1) with cobalt nanoparticles:Your work:(a) K (r = 10–8 m) =(b) K (r = 10–9 m) =Official English version.

Problem
2

Name: _______________

Quest. 1.1 1.2 2.1 2.2 3.1 3.2 3.3 3.4 3.5

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PointsStudent code: _________

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2281242152

32

2.2.1 Minimum water content in the mixture:
Your work:(a) H2O%(bulk Co) =(b) H2O%(nanoparticles with r = 1⋅10–9 m) =2.2.2

The correct answer is (mark the proper box):
(a)

(b)

(c)

2.3.1 Standard molar Gibbs function of CoO (external layer)

G 0 (CoO, rb ) =2.3.2

Standard molar Gibbs function of Co (internal layer):G 0 (Co, ra , rb ) =2.3.3 Standard Gibbs energy for the reaction (1) with the double-layered nanoparticles∆ r G 0 (1, ra , rb ) =Official English version.

Problem
2

Name: _______________

Quest. 1.1 1.2 2.1 2.2 3.1 3.2 3.3 3.4 3.5

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2281242152322.3.4. Plot ∆rG0 (1,r0) vs. r0(b)∆rG (1,r0)00∆rG (1,r0)(a)r0r0(d)∆rG(1,r0)∆rG(1,r0)

(c)

r0r0

The correct plot is (mark the proper box):
(a)

2.3.5

(b)

(c)

(d)

The correct answer is (mark the proper box):
(a)

(b)

(c)

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Problem3

Name: _______________

Quest. 1.1 1.2 2.1 2.2 3.1 4.1

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PointsStudent code: _________

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19.5

72

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4333

3.1.1 The overall reaction equation

The kinetic equation for X
d [X]
=dt

3.1.2 The rate equation
Your work:d [P]=dt
Reaction orders:with respect to B (i): ______
with respect to D (ii): ______
overall (iii): ______

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Problem3

Name: _______________

Quest. 1.1 1.2 2.1 2.2 3.1 4.1

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PointsStudent code: _________

Marks

19.5

72

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4333

3.2.1 1) An open system, [X]0 > k2/k1[X][X]0t2) An open system, [X]0 < k2/k1
[X]

[X]0t

3.2.2 A closed system, [B]0 = [D]0, [X]0 > k2/k1
[X]

[X]0t

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Problem3

Name: _______________

Quest. 1.1 1.2 2.1 2.2 3.1 4.1

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PointsStudent code: _________

Marks

19.5

72

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43

3

3

3.3.1

X–
Y–
P–

C2 H 6 + X + ... → 2X
X + Y → 2Y + ...
C2 H 6 + Y + ... → 2P
3.4.1 The highest possible temperature:Your work:

T=Official English version.

Problem
4Name: _______________

Quest. 1 2

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4 5.1 5.2

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2.25 13.5

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4.1. Equation:

4.2.1. Calculation of the T value:Your work:

T = _______________ mg/mL

4.2.2. Calculation of the T value:Your work:

T = _______________ mg/mL

4.2.3. Calculation of the T value:Your work:

T = _______________ mg/mLOfficial English version.

Problem
4

Name: _______________

Quest. 1 2

3.1

3.2

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2.25 13.5

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4.3. Equation(s):4.4.1 Equation(s):4.4.2. Equation:

4.4.3. The composition of the crystallohydrate is:Your work:

Formula of the salt Fe2(SO4)3·xH2O:

x = _____________

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Problem5

Name: _______________

Quest. 1.1

1.2

1.3

2.1

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51030

1010575

7.5

5

5.1.1 Structure of product D

5.1.2 Which class of organic compounds does D belong to? Check the appropriate box.
Note! Only one checkmark is allowed. Several checkmarks will lead to 0 marks for this question.
ketonesethersacetals
estersalcohols
aldehydes
glycols







5.1.3 The expected yield of D
The yield is equal to 85% ; lower than 85% ; greater than 85% Your work:yield =%5.2.1 The structures of A, B, and C.

ABC

5.2.2 Draw in the boxes intermediate compounds formed during the acidic hydrolysis of C, andbasic hydrolysis of B.
CB

H+/H2Ot

OH–/H2O

OH–/H2O

CH3COOH + C2H5OH

CH3COO– + C2H5OH

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Problem5

Name: _______________

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5

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5

5.3.1 The structure of senecioic acid

5.3.2 The structure of E.

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Problem
6

Name: _______________

Quest. 1.1 1.2 2.1 2.2 2.3 2.4 3.1 3.2

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37

7392231053

6.1.1 The net ionic equation accounting for the ability of LGL to set in air

6.1.2 Write down the net ionic equations matching the processes enumerated in the Table. For
each process check the “Yes” box if it leads to changes of pH. Otherwise check the “No” box.
а) protonation of ortho-silicate ions leading to the formation of Si-OH groups
Reaction equation:Yes4-Nob) formation of hydrated [SiO4(H2O)2] anions
Reaction equation:Yesc) polycondensation of ortho-silicate ions leading to the formation of Si-O-Si bonds
Reaction equation:
YesNoNo

6.2 For [Si3O9]n- ion found in aqueous solution of silicates:
6.2.1 Determine the charge (n).
Your justificationn = ______
6.2.2 Determine the number of oxygen atoms bridging adjacent tetrahedra.
Your justification

Number of oxygen atoms = ______
6.2.3 Depict the ion structure joining together several tetrahedra (1).

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Problem
6Name: _______________

Quest. 1.1 1.2 2.1 2.2 2.3 2.4 3.1 3.2

Tot

PointsStudent code: _________

Marks377392231053

6.2.4 The fragment of the layered structure joining 16 tetrahedra (1)Your justification

Structure

6.3.1 pH of 0.1 M aqueous solution of copper sulfate
Your justification

pH = _______
6.3.2 Equation of a reaction between aqueous solutions of CuSO4 and sodium metasilicate (LGL)

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Problem
7

Name: _______________

Quest. 1.1

1.2

2.12.22.3

2.4

2.5

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Marks

125

127

8.5

16

72.5

7.5

12

7.1.1 A number of reaction types is listed in the table below. All reactions involved inmetabolism of HMG-CoA to IPP are in the list. Choose those types of reactions which arecatalyzed by Е1 and Е3 (put numbers in appropriate places).
NoReaction type1.
Dehydration2.
Decarboxylation
3.
Dephosphorylation
4.
4 electron reduction
5.
Release of the reduced form of coenzyme A (CoA-SH)
6.
Monophosphorylation
7.
Oxidation of hydroxyl group as the third stage of HMG-CoA β-oxidation cycle
Е1_______________

Е3_______________

7.1.2 Draw the structure of X with stereochemical details and indicate absolute configuration (Ror S) of the stereocenter.

7.2.1 Write down the overall reaction equation for reductive ozonolysis of DAP with dimethyl
sulfide used as the reducing agent.

7.2.2 Determine molecular formula of Y.

Your justification

Number of carbon atoms_______
Number of hydrogen atoms_____

Molecular formula:________________
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Problem
7Name: _______________

Quest. 1.1

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127.2.3 Calculate the number of IPP and DAP molecules needed to give Y5.
Your justification:

Number of IPP molecules ____

Number of DAP molecules ____

7.2.4 Draw the product of coupling reaction between one IPP molecule and one DAP molecule,subsequent reductive ozonolysis of which gives Y1, Y2 and one more product, the latter
containing phosphorus.

7.2.5 Draw the structures of Y and Y4 with stereochemical details.

Y4Y

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Problem
8Name: _______________

Quest.

1.1 1.2 2.1 2.2 2.3

Student code: _________

Marks

895

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11 14 16.5 12 10

13.5

99

8

8.1.1 Expressions for the rates:

vact =

vp =vdeact =vt =8.1.2 Compare rates using operators <<, ≤, ≈, ≥, >>vdeactvact

vdeactvp

vdeactvt

8.2.1 Mass of the obtained polymer.
Your justification:

m=8.2.2 Degree of polymerization of the obtained polymer.
Your justification:

DP =Official English version.

Problem
8Name: _______________

Quest.

1.1 1.2 2.1 2.2 2.3

Student code: _________

Marks

895

3.1

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11 14 16.5 12 10

13.5

99

8

8.2.3 Structure of the obtained polymer.

8.3.1 Fill in the right column with symbols (a-g) of 1H NMR signals corresponding tosubstructures in the left column.
*CH2O

*CH2

*
H

H

H

H
H
*

H

H

H

H
*

*
*H
*

ClClH

H

8.3.2 Composition and molecular weights of copolymers P1 and P2.
Your justification:
Your justification:n(C) =n(D) =M(P1) =

M(P2) =
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Problem
8Name: _______________

Quest.

1.1 1.2 2.1 2.2 2.3

Student code: _________

Marks

8

95

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3.4

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11 14 16.5 12 10

13.5

99

8

8.3.3. All possible reactions of activation
P1:

P2:

8.3.4 Structure of P1 and one of possible structures of P2
P2:
P1:

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