25

th
Austrian Chemistry Olympiad 1999
National Competition Theoretical Part - Solutions

Problem 1: 7 b.p. = 4 r.p.; f = 0,57143

Complex Chemistry

1 b.p. each






Y
Y
Y
Y Y
Y
stab.
Y
Y
Y
Y Y
Y
25
th
Austrian Chemistry Olympiad 1999
National Competition Theoretical Part - Solutions
Problem 2: 39 b.p. = 11r.p.; f =0,28205

Environmental and Inorganic Chemistry

A. Determination of oxygen in a sample of water from the river Schwechat

Task 1:
1
st
step: 2Mn
2+
+ O
2
+ 4OH
-
2 MnO(OH)
2
1 b.p.
2
nd
step: 2MnO(OH)
2
+ 2Mn
2+
+ 8H
+
4Mn
3+
+ 6 H
2
O 1 b.p.
3
rd
step: 4Mn
3+
+ 4I
-
2I
2
+ 4Mn
2+
1 b.p.
4
th
step: 2I
2
+ 4S
2
O
3
2-
2 S
4
O
6
2-
+ 4I
-
1 b.p.

Task 2:
a) IO
3
-
+ 6S
2
O
3
2-
+ 6H
+
I
-
+ 3H
2
O + 3S
4
O
6
2-
2 b.p.

b)

3 b.p.



c) n(O
2
) = 0.25*c(S
2
O
3
2-
)*V(S
2
O
3
2-
) = 0.25*9.841*10
-3
*11.80 = 2.903*10
-2
mmol in
103.50mL
L mg O / 976 . 8 00 . 32 *
50 . 103
10 * 903 . 2
) (
2
2
= =

| 2 b.p.
d) % 9 , 98 100 *
08 . 9
976 . 8
SSI = = 1 b.p.
e) n(O
2
) = 0.25*c(S
2
O
3
2-
)*V(S
2
O
3
2-
) = 0.25*9.841*10
-3
*6.75 = 0.0166 mmol in 102.20 mL
L mg O / 20 . 5 00 . 32 *
20 . 102
0166 . 0
) (
2
= = | 1 b.p.

f) BSB
5
= 8.976 5.20 = 3.78 mg/L O
2
1 b.p.

B. The peculiar chemistry of a well known element

Task 1:

Element Phosphorus 1 b.p.
[Ne]3s
2
3p
3
1 b.p.

Task 2:







1 b.p. 2 b.p. 2 b.p. 2 b.p.

L mol IO c
L mol
O S V
IO V IO c
O S c
/ 10 * 168 . 8
0 . 214
10 * 8 . 174
) ( with
/ 10 * 841 . 9
) (
) ( ). ( . 6
) (
4
3
3
3
2
3 2
3 3 2
3 2

= =
= =
P
H
H
H
H
P
H
P
H
H
H
P
H
P
P
H
H
H
H
P
H
P
P
H
P
H
H
H 1
2
3 4
25
th
Austrian Chemistry Olympiad 1999
National Competition Theoretical Part - Solutions
Task 3:
Compound Nr. 4 1 b.p.

Task 4:








3 b.p. 3 b.p. 3 b.p.

Task 5:

a) 3NH
4
Cl + 3PCl
5
(NPCl
2
)
3
+ 12HCl 2 b.p.
b)



2 b.p.




Task 6:

Heating rapidly the substance melts without breaking of the ring
Heating slowly rings are cracked polymer molecules are formed with a conjugated t-
system:

2 b.p.






OH
p
H
H
O
OH
p
OH
OH
O
OH
p
H
OH
O
+I
+III +V
p
N
p
N
p
N
Cl
Cl
Cl
Cl
Cl Cl
N
P
N
P
N
P
Cl
Cl Cl Cl
25
th
Austrian Chemistry Olympiad 1999
National Competition Theoretical Part - Solutions
Problem 3: 5 b.p. = 5r.p.; f =1,00000

Cerimetric analysis

Ionic equation:

AsO
3
3-
+ 2 Ce
4+
+ H
2
O 2 Ce
3+
+ AsO
4
3-
+ 2H
+
1 b.p.

V
E E
E E
Ce c
Ce c
Ce c
Ce c
Ce c
Ce c
E E
Ce c
Ce c
AsO c
AsO c
AsO c
AsO c
Ce c
Ce c
E E
AsO c
AsO c
Ce c
Ce c
E E
E E E
Ce c
Ce c
E E
AsO c
AsO c
E E
AsO c
AsO c
H c E
AsO c
H c AsO c
E E
eq
90 , 0
3
059 . 0 * 2 2
E
: yields E in on substituti
) 059 . 0 ( * 059 . 0 *
3
2
) (
) (
log further and
) (
) (
log
2
059 . 0
) (
) (
log 059 . 0 059 . 0 : gains on substituti
) (
) (
) (
) (
: point equivalent at
) (
) (
log
2
059 . 0
) (
) (
log 059 . 0 059 . 0
) (
) (
log
2
059 . 0
) (
) (
log 059 . 0 059 . 0
) (
) (
log 059 . 0
) (
) (
log
2
059 . 0
059 . 0 : 1 pH fr
) (
) (
log
2
059 . 0
) ( log
2
059 . 0
) (
) ( * ) (
log
2
059 . 0
0
1
0
2
eq
2
0
2
0
1
3
4
3
4
3
4
0
2
0
1
3
4
3
4
3
3
3
4
3
3
3
4
0
2
0
1
3
3
3
4
3
4
0
2
0
1
2 1
3
4
0
2 2
3
3
3
4 0
1 1
3
3
3
4 2 0
1
3
3
2 3
4 0
1 1
=
+
=
=
+ =
=
+ =
=
= =
+ =
+ = =
+ + = + =
+
+
+
+
+
+
+
+

+
+

+
+
+
+

+

4 b.p.


25
th
Austrian Chemistry Olympiad 1999
National Competition Theoretical Part - Solutions
Problem 4: 19 b.p. = 7 r.p.; f = 0,36842

Physical Chemistry

A. Vapour pressure of a mixture

M(EtAc) = 88.11 g/mol; M(EtPr) = 102.1 g/mol;
N(EtAc) = 0.284 mol; n(EtPr) = 0.490 mol; En
i
= 0.774 mol; 3x1 = 3 b.p.
x(EtAc) = 0.367; x(EtPr) = 0.633; 2x1 = 2 b.p.
p(EtAc) = 3562 Pa; p(EtPr) = 2338 Pa; 2x1 = 2 b.p.
p
g
= 59 hPa 1 b.p.

B. A kinetic problem

a) Write a balanced equation for this substitution.

CH
3
Br + OH
-
CH
3
OH + Br
-
1 b.p.

b) Determine the reaction order relative to the individual starting substances and also the
overall reaction order using a calculation.

Relative to KOH: 0.17 : 0.10 = 1.7
4.76 : 2.80 = 1.7 1
st
order 1 b.p.
Relative to CH
3
Br: 0.20 : 0.10 = 2 v
o
should be 5.60*10
-6
mol/L.s
1.85:5.60 = 0.33
0.33:0.10 = 0.033 1
st
order 2 b.p.
Overall: 2
nd
order 1 b.p.

c) Calculate the velocity constant of the reaction.

v = k*c(CH
3
Br)*c(OH
-
) s mol L k . / 10 8 . 2
1 . 0
10 8 . 2
4
2
6

- =
-
= 2 b.p.

d) How long will it last to reach a concentration of KOH of 0,05 mol/L in the first
experiment?

There are 0.05 mol/L OH
-
and 0.05 mol/L CH
3
Br in the reaction vessel, both means c
o
/2!
Therefore t = t
For a second order reaction with c
o
(A) = c
o
(B) we have:
s
c k
o
35714
1 . 0 10 8 . 2
1 1
4
=
- -
=
-
=

t
t = 9.9 h 3 b.p.

e) Give the more accurate name of the mechanism which may possibly apply to the reaction.

S
N
2 1 b.p.


25
th
Austrian Chemistry Olympiad 1999
National Competition Theoretical Part - Solutions
Problem 5: 24 b.p. = 7 r.p.; f = 0,29167


Thermochemistry

a) Calculate the formation enthalpies AH
u
298
of the compounds hydrazine, dinitrogenoxide
and ammonia.

We look for AH
u
298
for: N
2
+ 2 H
2
N
2
H
4


-(1) + 3.(2) + (3) (4) gives: 4 N
2
+ 8 H
2
4 N
2
H
4
4 b.p.

AH
u
298
= 203 kJ/4 mol AH
u
298
= 50.8 kJ/mol 2 b.p.

from (2): 317 = AH
u
298
(N
2
O) + 0 - 50.8 + 286 AH
u
298
(N
2
O) = 81.8 kJ/mol 2 b.p.

from (3): -143 = 50.8 - 286 -2* AH
u
298
(NH
3
) AH
u
298
(NH
3
) = -45.6 kJ/mol 2 b.p.

b) Write a balanced equation for the combustion of hydrazine to give water and nitrogen.

N
2
H
4
+ O
2
N
2
+ 2 H
2
O 1 b.p.

c) Calculate the reaction heat of the above combustion at constant pressure and at 298 K.
Also calculate AG
u
298
and K
th
.

AH
u
298
= -2*286 - 50.8 = -623 kJ 2 b.p.

AS
u
298
= 191 + 2*66.6 - 205 -240 = -121 J/K 2 b.p.

AG
u
298
= -623 + 298*0.121 = -587 kJ 2 b.p.

103 4343 . 0 237 K log 237 K ln
th th
237
298 314 . 8
587000
= - = = = =
-
e e K
th


K
th
= 10
103
3 b.p.

d) What will be the reaction heat of reaction #3 at constant volume, if one starts with 2 mol
ammonia and 0,5 mol oxygen?

AH = AU + p*AV = AU + An*RT

AU = AH - An*RT; An = 1 2.5 = - 1.5

AU = -143000 + 1.5*8.314*298 AU = -139 kJ 4 b.p.



25
th
Austrian Chemistry Olympiad 1999
National Competition Theoretical Part - Solutions
Problem 6: 12 b.p. = 6 r.p.; f = 0,50000

Ionic Equilibrium

a) Calculate the concentration of Ag
+
.

M(AgNO
3
) = 169.9 g/mol mol/L 010 . 0
5 . 0 9 . 169
85 . 0
=
-
=
o
c 1 b.p.

b) Write a balanced equation for the formation of the complex.

Ag
+
+ 2 NH
3
[Ag(NH
3
)
2
]
+
1 b.p.

c) Calculate the equilibrium concentration of free silver.

Dilution: c
o
(Ag
+
) = 0.0050 mol/L; c
o
(NH
3
) = 1.0 mol/L 2 b.p.

|([Ag(NH
3
)
2
]
+
) = 1/K
D
= 1.69*10
7
L
2
/mol
2
>> 1

mol/L 10 3.0 x
1
005 . 0
10 -
2
- =
-
~
x
| 3 b.p.

d) Calculate the equilibrium concentration of [Ag(NH
3
)]
+
using the data from c).

Ag
+
+ NH
3
[Ag(NH
3
)]
+


mol/L 10 5.4 x
1 10 . 3
7 -
10
1
- =
-
=

x
K 3 b.p.

e) What is the value for K
2
of the reaction: [Ag(NH
3
)]
+
+ NH
3
[Ag(NH
3
)
2
]
+
?

L/mol 10 4 . 9 K
3
2
1
2 2 1
- = = - =
K
K K K
|
| 2 b.p.





25
th
Austrian Chemistry Olympiad 1999
National Competition Theoretical Part - Solutions
Problem 7: 40 b.p. = 20 r.p.; f = 0,50000

Organic Chemistry


Problem 7A:

a) 8 b.p.






b) 9 b.p.







c) A
E
(1,4-addition) 2 b.p.

d) Because an aromatic (more stable) compound is formed. 1 b.p.



O
O
Cl
Cl Cl
Cl
O
O
+ HCl
O
OH
Cl
H
OH
OH
Cl
+ 1/2 O
2
- H
2
O
O
O
Cl
25
th
Austrian Chemistry Olympiad 1999
National Competition Theoretical Part - Solutions
Problem 7B:

1.









































A,B,C,D,H ..... 1 b.p. each
E,F,G,I,K ...... 2 b.p. each
2. Optical activity. 1 b.p.
3. A B: electrophilic addition; B C: nucleophilic substitution 2 b.p.
4. For instance: 2 b.p.










F
C
A
B
H
D
G
E
I
K
Br
CN
COOH
OH
O
N
NH
OSO
3
H
O
SO
2
O
O
C
2
H
5
CH
3
HO
H
25
th
Austrian Chemistry Olympiad 1999
National Competition Theoretical Part - Solutions

Problem 8: 28 b.p. = 9 r.p.; f = 0,32143

Biochemistry

Problem 8A:

a) The oxidized form has another tertiary structure. 1 b.p.

b) A restrictionsendonuclease. 1 b.p.

c) 5-GCCGTGCTTAAA-3 6 b.p.

d) Repair enzymes will reconstruct the original sequence. 1 b.p.

e) The mutant is not resistant against special antibiotics. 1 b.p.

f) Ala-Val-Leu-Lys 3 b.p.

g) CH
3
CH(NH
2
)-CO-NH-CH[CH(CH
3
)
2
]-CO-NH-CH[CH
2
CH(CH
3
)
2
]-CO-
-NH-CH[CH
2
CH
2
CH
2
CH
2
NH
2
]-COOH 3 b.p.




Problem 8B:

* Phe ; UUU 3 b.p.

* Val, Leu and Cys contain 2x U and 1x G in their codons. 3 b.p.
It is not possible to determine the sequence of bases within the codon. 1 b.p.
Trp and Gly contain 1x U and 2x G in their codons. 2 b.p.
The other amino acids have codons containing A and C. 3 b.p.