Student code:

XIX Baltic
Chemistry
Olympiad

Theoretical Problems
Answer sheets

Code: ....................

1. 2. 3. 4. 5. 6. Σ

15-17 April 2011

Vilnius, Lithuania
Student code:
Problem 1. Aluminium
a)
Calculations:
n=9.48 g / 474 g/mol = 0.0200 mol
m(H2O)= 100 + 0.02*12*18 =104.32 g
cm=0.0200 mol/0.10432 kg=0.1917 mol/kg
ΔT = -4*1.86 ˚C kg/mol *0.1917 mol/kg = -1.43 ˚C

Freezing point is: __-1.43 ˚C __

b)
Molecular equation:
Al2O3 +2NaOH + 3H2O  2Na[Al(OH)4]

c)
Calculations:
Ksp is so small that main source of OH- is water, not Al(OH)3. So we can assume that [OH-] =
1.0*10-7.
Al(OH)3  Al3+ + 3OH-
x 1.0*10-7

1.3·10–33 = x*(1.0*10-7)3 x= 1.3*10-12

Will dissolve 1.3*10-12 *10 =1.3*10-11 mol  m = 1.0*10-9 g of Al(OH)3

Mass = __1.0*10-9 g __
Student code:
d)
Calculations:
n(EDTA) = 0.0500 M *50.00 mL = 2.5 mmol
n(Zn2+) = 0.0500 M *23.25 mL = 1.1625 mmol
n(Al3+) = 2.5-1.1625 = 1.13375 mmol

c=1.13375 mmol / 20.00 mL = 0.0669 mol/L

e)
Isomers:

f)
Al2Cl6 molecule
Student code:
Problem 2 Beware of light!
1. Formulas for compounds:
A KI E I3 -
B KOH F Cl2
C I2 G KIO3
D KI3
Reaction 1: 5KI + 2H2O + O2  4KOH + I2 + KI3

Reaction 2: KI + I2  KI3

Reaction 3: 6KOH + KI + 3Cl2  KIO3 + 6KCl + 3H2O

Reaction 4: KIO3 + 5KI + 6H+  3I2 + 6K+ + 3H2O

Reaction 5: 2KIO3 + 12HCl  I2 + 5Cl2 + 2KCl + 6H2O

2. Mark correct answer(-s):

A B C D E
X X
3. Solubility is higher due to ... Solubility increases due to formation of complex anion I3-.

4. Lewis formula for E

5.
KIO3 + 5KI + 6H+  3I2 + 6K+ + 3H2O
IO3- + 6H+ + 5e-  ½I2 + 3H2O Eo = 1,195 V (1)
½I2 + e-  I- Eo = 0.536 V (2)

Nernst equation for reduction halfreaction:

RT cred
E  Eo  ln
zF coks
E for halfreaction (2):
RT [ I  ] 8,314  298
E2  E o 2  ln  0,536  ln( 0,10)  0,595V
zF 1 1  96485
E for halfreaction (2), as a function of pH:
RT 1 RT 1 RT 1
E1  E o1  ln 
 E o
1  ln  ln 
zF [ IO3 ]  [ H  ]6 zF [ IO3 ] zF [ H  ]6


RT 1 RT 8,314  298 1 8,314  298

E o1  ln 
 2,303  6  pH  1,195  ln  2,303  6  pH 
zF [ IO3 ] zF 5  96485 0,25 5  96485
 1,188  0,0710 pH
pH, when E1 = E2:
0,595  1,188  0,0710 pH
1,188  0,595
pH   8,35
0,071
Student code:
6. Reaction equation for reaction of A with persulphate:
2I- + S2O82-  2SO42- + I2

7. Partial rate orders: _1_ with respect to A and _1_ with respect to S2O82-.

2
Kinetic equation: rate = k  [ I  ][S 2O8 ]

Reaction rate constant calculations:

v 1.1  10 8
Rate constant: k =    0.011 L/(mols)
[ I ][S 2O82 ] 0.1  10  106

8. Temperature calculations:
Reaction rate increases due to change of rate constant. Using Arrehinus equation:

k 25 E A  1 1 
ln    
kT R  TT T25 
k 25 42 000  1 1 
ln      ln 0.1
10  k 25 8.314  TT 298 
1 1 8.314  ln 0.1
   4.558 10 4
TT 298 42 000
1 1
 4.558 10 4   2.9 10 3
TT 298
T  344.8 K  345 K  72 o C
9. Reaction time calculations:
For calculations use second order rate equation (as concentrations for all reactants are equal):
1 1
  k t
C C0
1 1
3
  0.011 t
0.1  10 1  103
t  818181s  227 h  230 h
Reaction time is ___230 ____ hours.
Student code:
Problem 3 Reacting gas
a) 3H2 + N2 = 2NH3
b)
3H2 N2 2NH3 Σ
t=0 n0 n0 0
t = ∞ n0 − 3yn0 n0 − 3yn0 2yn0 2n0 − 2yn0
x∞ n0  3 yn0 1 3y n0  yn0 1 y 2 yn0 2y 1
  
2n0  2 yn0 2  2 y 2n0  2 yn0 2  2 y 2n0  2 yn0 2  2 y
2y
xNH3 
2  2y
2 2
pNH xNH p2 (2  2 y ) 2  4 y 2 1 16  (1  y )  y 2
Kp  3 3
 3 3 3
  
pH2 pN2 xH2 p xN2 p (1  3 y )3  (1  y) p 2 (1  3 y )3 p 2

c)

2y 2  0.1111
xNH3   0.1111  y   0.1000
2  2y 2  2  0.1111
16  (1  y )  y 2 16  (1  y )  y 2 16  0.9  0.12
Kp   p    51.2 bar
(1  3 y )3 p 2 (1  3 y ) 3 K p 0.7 3  1.60  10 4 bar 1

d)

A No B Yes
Calculations:
2H2 + CO = CH3OH
pCH3OH
 r G   r G  RT ln 2

99pCH3OH  10 pCH3OH 
1
 21.21 kJ / mol  4.157 kJ / mol  ln 2
 2.11 kJ / mol
9900   0.1
Methanol would not form, equiligrium is shifter towards the production of reagent.

 r G   r G  RT ln Q

e)

  G
Q  exp   r   Qmax  0.00608
 RT 
Q is maximal value, below this value methanol production is favorable.
Student code:
Problem 4 Smart robot
a)
AP B PCl5 C H3PO4 D HCl
b)

b) Equations
1 2P + 5Cl2 = 2PCl5
2 PCl5 + 4H2O = H3PO4 + 5HCl
3 HCl + NaOH = NaOH + HCl
4 H3PO4 + 3NaOH = Na3PO4 + 3H2O
c)

If A and NaOH relate through a set of equactions as 1:x, then

m mx 10.0 mg  x g
M (A)    3
 4.062 x
n Vc 0.1234 M  19.95 cm mol
According to gas diffusion results sample contains two isotopes in equimolar quantities. Let
their masses me M1 and M2, then
4.92 mg 5.08 mg M  M2 g
 and 1  4.062 x
M1 M2 2 mol
For x = 8 we have M1 = 32 g/mol and M2 = 33 g/mol. A is phosphorus.
5HCl + H3PO4 + 8NaOH = Na3PO4 + 8H2O + 5NaCl (x = 8)

d)

a1 M 1 5.19  1013 s 1  32 g / mol

k1    5.61  107 s 1
m1 N A 0.00492 g  6.02  10 23 mol1
a2 M 2 2.94  1013 s 1  33 g / mol
k2    3.17  107 s 1
m2 N A 0.00508 g  6.02  1023 mol1
Initial a0 = a1 + a2. final activity is af = 0.001a0 and almost entirely due to decay of 33P as this
isotope has a smaller constant of decay. Therefore,
af  0.001a0  k2 N 2 exp  k2 t 
1  0.001a0 
t ln   215
k2  k2 N 2 
1  0.001   5.19  1013  2.94  1013  s 1  33 g / mol 
t ln    1.86  107 s  215 d
3.17  107 s 1 7 1
 3.17  10 s  0.00508 g  6.02  10 mol  23 1
 

Time = __215 d___

e)

E: S F: SCl2 G: H2S H: H2SO3

Student code:
f) Chemical equations:

1 2S + Cl2 = S2Cl2

2 S2Cl2 + 2H2O = H2S + 2HCl + SO2

3 H2S + 2NaOH = Na2S + 2H2O

4 SO2 + 2NaOH = Na2SO3 + H2O

5 HCl + NaOH = NaOH + HCl

Radioactive decy equations:

32
1 P = 32S + e− + 
33
2 P = 33S + e− + 

g)

Calculations:

If E and NaOH relate through a set of equactions as 1:y, then

m mx 10.0 mg  y g
M ( E)    3
 10.83 y
n Vc 0.4321 M  2.136 cm mol
Therefore, y = 3. Thus F can only be S2Cl2.
½H2S + HCl + ½H2SO3 + 3NaOH = ½Na2S + NaCl + ½Na2SO3 + 3H2O
Student code:
Problem 5. Chiral polyhydroxylated cyclohexanoids.
1. Which class of enzymes will catalyze this reaction? (select the appropriate class of
enzymes)
a) oxidoreductase
b) isomerase
c) lipase
d) ligase

2. What is the maximum yield of compound B?

a) 100 %

b) 90 %

c) 75 %

d) 50 %

3. Find chiral centers of compound B and indicate their configurations.

MeO OMe
Cl
Cl
(S)

(S) (R)
Cl Cl
OCOMe
Student code:

4. Draw the entire structures of compounds D-G.

D: E:

F1: F2:

G1: G2:

5. In respect to each other compounds G1 and G2 are:

a) enantiomers

b) structural isomers
c) diastereomers

d) conformers.
Student code:
Problem 6. Flat carbon

Answers