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FINAL

2011
ROUND, PROBLEMS

Solve all problems provides. Fill answer sheets and till 13:00, March 20, 2011 send them to email:
kimijas_olimpiades@inbox.lv You will receive answer that your solutions are received and will be graded in few
days.
This round consists from two parts. Part A 60 multiple choice questions with one correct answer each.
Maximum points for this round is 30 points. Part B 6 short answer problems. Each problem is graded with
maximum5points.Pointsforfinalroundareaddedtopointsgainedinfirstthreerounds.

PartAMultiplechoicetest
Chooseonecorrectanswerforeachquestionandwritecorrespondingletterinanswersheetprovided.
Question1

Question2

Question3

Question4

Question5

Question6

Question7

Question8

Question9

Time,s

Question10

Question11

Question12

Question13

Question14

Question15

Question16

Question17

Question18

Question19

Question20

Question21

Question22

Question23

Question24

Question25

Question26

Question27

Question28

Question29

Question30

Question31

Question32

Question33

Question34

Question35

Question36

Question37

Question38

Question39

Question40

Question41

Question42

Question43

Question44

Question45

Question46

Question47

Question48

Question49

Question50

Question51

Question52

Question53

Question54

Question55

Question56

Question57

Question58

Question59

Question60

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FINAL

2011
ROUND, PROBLEMS

PartBShortanswerquestions
Problem1
Chemicalcrosswordinorganicchemistry(8points)
LettersA,B,Dect.standsforunknowninorganiccompounds,whichreactasshownintable.Formulasforall
organiccompoundsareknown.

CompoundAcontainstransitionmetalandtransitionmetalcontentisapproximately72%(bymass)
SolutionsofcompoundsU,N,arestronglybasic.Therearenoinformationaboutsolutionsofother
compounds.
SolutionsofcompoundsOandNcolorsgasflameyellow,whilecompoundsUuncolorsflamepurple
red.
WatersolutionsofcompoundsV,PandLareblue.
SubstancesE,G,H,M,R,S,containonlyonechemicalelement.
Threetransitionmetalsarementionedinthiscrossword.
Equationsincrosswordarenotbalanced.

Writechemicalformulasforallcompoundsabbreviatedwithletters.
A
+
E

F
+
G

E
+
U

F
+
T

+
+

I
+
H

L
+
N

O
+
P

G
+
J

E
+
K

R
+
Q

+
E

C2H5NO2 +

D
+
H

M
+
Q

+ F
+
V +
+
W
I

D
+
R

B
+

I
+
E

U
+
F
+

+
E

C2H5Cl

+
F

Z
+
F

C2H6 +
Y
+

+
C
H

2 5OH

C2H6
+

+
CH3Cl
I

+
D

+
I

G
+
E

+
Y

C2H4

C2H6

Problem2
Useofmathtodescribechemicalprocessesphysicalchemistry(10points)

Problem3
Someorganicchemistry(6points)

Problem4
Complexformationandredoxproperties(6points)
You have to investigate 1st type electrode using software MS Excel (or analogue). The first type electrode
consistsfrommetal(M(s))anditsionsinsolution(Mx+(aq)).Thistimesolutionalsocontainprotolyticpairfrom
whichconjugatedbaseactsasligandsandformcomplexionswithMx+.
DrawgraphtoshowhowreductionstandardpotentialisdependentonpHiffreeligandconcentrationin
solutionisa)0.1M,b)1.0Mand5.0M.

Givenelectrode:
Cu2+(aq)+2eCu(s)
Eo=+0.345V
+

pKa(NH4+)=9.25
Ligands:

NH3/NH4
Summarycomplexformationconstants:

lg1=3.99

lg1,2=7.33

lg1,2,3=10.06

lg1,2,3,4=12.03

lg1,2,3,4,5=11.43

lg1,2,3,4,5,6=8.9
Hints:
1. Assumethatconcentrationsumforconjugateacidandbaseandacidareconstant(ifbaseareusedfor
complexformationitisaddedtosolutiontomaintainconstantconcentrationorconcentrationofbase
ishugeenoughandstaysalmostconstant).

2. Writemathematicalequationsforcalculationrealreductionstandardpotentialsdependingfrommolar
fractionofmetalionsinsolution.
Example:

3. UsingMSExcelprogramcalculaterealstandardpotentialvalues,ifpHchangesfrom0to14(step0.5).
Madecalculationinthreecases:a)conjugateacidandbaseconcentrationsumisCL=0.1M,b)CL=1
Mandc)CL=5M.Allcalculationresultscollectintable.

www.biosan.lv

FINAL

PartAMultiplechoicetest
Q.number
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
33.

Answer
B
B
D
Nocorrectanswer,D,allstatementsaretrue
A
32.
B
A
33.
D
B
34.
A
A
35.
A
D
36.
B
C
37.
B
D
38.
C
A
39.
D
B
40.
A
A
41.
D
B
42.
B
D
43.
C
A
44.
B
B
45.
A
B
46.
D
B
47.
A
C
48.
A
C
49.
B
D
50.
B
A
51.
B
B
52.
D
A
53.
D
C
54.
A
B
55.
A
B
56.
C
C
57.
C
A
58.
A
B
59.
C
D
60.
B

2011
ROUND, SOLUTIONS

PartBShortanswerquestions
Problem1
Chemicalcrosswordcorrections(madewithredcolor)
A
+
E

F
+
G

E
+
U

F
+
T

+
+

I
+
H

L
+
N

O
+
P

G
+
J

E
+
K

R
+
Q

+
E

D
+
H

M
+
Q

+ F
+
V
+

+
W
I

C2H5Cl

+
F

C2H5NO2 +

D
+
R

B
+

I
+
E

U
+
F
+

+
E

C2H6
+

S
+
CH3Cl

+
F(notI)

(notG)

Z
+
F

+
Y

+ C2H5OH

C2H6

+
D

+
E

C2H4

C2H6

Answers:
AFe3O4orotheroxidewhichcontains72%metal,Mn3O4,Rh2O5,CaOisnotacceptedwrongchemistry
BCO
DCO2
EH2
FH2O
GFe
HC
IO2
JHCl
KFeCl2
LCuCl2
MCu
NNaOH
ONaCl
PCu(OH)2
QH2SO4
RZnorothermetal
SLiorotheralkalimetal
TLiHorotheralkalimetal
ULiOHorotheralkalimetal

VCuSO4
WSO2
ZNO2
YHNO3
CaH2,Caaccepted
ZnO
Al
H2CO3
Li[Al(OH)4]
Ca(OH)2
CaCO3
CaO
LiClorothermetal
ZnSO4

Problem2

Problem3

Problem4

Cu2++2eCu

0
red
=0,764V

Cu2++NH3

[Cu(NH3)]2+

lg 1 = 3,99

Cu2++2NH3

[Cu(NH3)2]2+

lg 2 = 7,33

Cu2++3NH3

[Cu(NH3)3]2+

lg 3 = 10,06

Cu2++4NH3

[Cu(NH3)4]2+

lg 4 = 12,03

Cu2++5NH3

[Cu(NH3)5]2+

lg 5 = 11,43

Cu2++6NH3

[Cu(NH3)6]2+

lg 6 = 8,9

NH4++H2O

H3O++NH3

pKA=9,25

= red

RT
RT
1
0
= red
+
ln
ln [Cu 2+ ]
2+
2 F [Cu ]
2 F

[ H 3O + ] [ NH 3 ]
K A =
+
[ NH 4 ]

C = [ NH + ] + [ NH ] + [{Cu ( NH ) }2+ ] + 2 [{Cu ( NH ) }2+ ] + 3 [{Cu ( NH ) }2+ ] +


4
3
3 1
3 2
3 3
L
+ 4 [{Cu ( NH 3 ) 4 }2+ ] + 5 [{Cu ( NH 3 ) 5 }2+ ] + 6 [{Cu ( NH 3 ) 6 }2+ ]

2+
K = [{Cu ( NH 3 )} ]
1 [Cu 2+ ] [ NH ]
3

[{Cu ( NH 3 ) 2 }2+ ]
K 2 = [Cu 2+ ] [ NH ]2
3

[{Cu ( NH 3 ) 3 }2+ ]
K 3 =
[Cu 2+ ] [ NH 3 ]3

[{Cu ( NH 3 ) 4 }2+ ]
K 4 =
[Cu 2+ ] [ NH 3 ]4

2+
K 5 = [{Cu ( NH 3 ) 5 } ]

[Cu 2+ ] [ NH 3 ]5

2+
K = [{Cu ( NH 3 ) 6 } ]
6 [Cu 2+ ] [ NH 3 ]6

2+
2+
2+
2+
2+
CCu = [Cu ] + [{Cu ( NH 3 )1} ] + [{Cu ( NH 3 ) 2 } ] + [{Cu ( NH 3 ) 3 } ] + [{Cu ( NH 3 ) 4 } ] +

2+
2+
+ [{Cu ( NH 3 ) 5 } ] + [{Cu ( NH 3 ) 6 } ]
+

C L = [ NH 4 ] + [ NH 3 ] + [{Cu ( NH 3 )1}2+ ] + 2 [{Cu ( NH 3 ) 2 }2+ ] + 3 [{Cu ( NH 3 ) 3 }2+ ] +


+ 4 [{Cu ( NH 3 ) 4 }2+ ] + 5 [{Cu ( NH 3 ) 5 }2+ ] + 6 [{Cu ( NH 3 ) 6 }2+ ]

CL = [ NH 4 ] + [ NH 3 ]


[ H 3O + ] [ NH 3 ]
K
=
A
[ NH 4+ ]

10 pH [ NH 3 ]
+
+

CL = [ NH 4 ] + [ NH 3 ] [ NH 4 ] = CL [ NH 3 ] K A =
CL [ NH 3 ]

10 pH [ NH ] = K C [ NH ] K (10 pH + K ) [ NH ] = K C
3
3
3
A
L
A
A
A
L

K A CL

[ NH 3 ] = 10 pH + K
A

[{Cu ( NH 3 ) }2 + ]
[{Cu ( NH 3 ) }2 + ]
K C

[{Cu ( NH 3 ) }2 + ] = 1 [Cu 2 + ] pHA L

=
1 =
1
2+
[Cu ] [ NH 3 ]
+ KA
K C
10

[Cu 2 + ] pHA L

+ KA
10

K A CL
[{Cu ( NH 3 ) 2 }2 + ]
[{Cu ( NH 3 ) 2 }2 + ]
2+
2+

2 =
[{Cu ( NH 3 ) 2 } ] = 2 [Cu ] pH
2 =
2
[Cu 2 + ] [ NH 3 ]2
+ K A

K A CL
10
2+

[Cu ] pH

+ K A

10

3
2+
= [{Cu ( NH 3 )3} ] K [{Cu ( NH ) }2 + ] = [Cu 2 + ] K A CL
3 3
3
10 pH + K
3 [Cu 2 + ] [ NH ]3
3
A

4
2+

K A CL
[{Cu ( NH 3 ) 4 } ]
2+
2+
4 =

K [{Cu ( NH 3 ) 4 } ] = 4 [Cu ] pH
[Cu 2 + ] [ NH 3 ]4
+ K A

10

5
K A CL
[{Cu ( NH 3 )5 }2 + ]

2+
2+
5 = [Cu 2 + ] [ NH ]5 K [{Cu ( NH 3 )5 } ] = 5 [Cu ] 10 pH + K
3
A

2+

A CL
6 = [{Cu2(+NH 3 )6 } 6] K [{Cu ( NH 3 )6 }2 + ] = 6 [Cu 2 + ] K
10 pH + K
[Cu ] [ NH 3 ]

2+
2+
2+
2+
2+
CCu = [Cu ] + [{Cu ( NH 3 )} ] + [{Cu ( NH 3 ) 2 } ] + [{Cu ( NH 3 )3} ] + [{Cu ( NH 3 ) 4 } ] +

2+
2+
+ [{Cu ( NH 3 )5 } ] + [{Cu ( NH 3 )6 } ]
CCu = [Cu 2 + ] + [{Cu ( NH 3 )}2 + ] + [{Cu ( NH 3 ) 2 }2 + ] + [{Cu ( NH 3 )3}2 + ] + [{Cu ( NH 3 ) 4 }2 + ] +
+ [{Cu ( NH 3 )5 }2 + ] + [{Cu ( NH 3 ) 6 }2 + ] =

2
3
4

1 + K a CL + K a CL + K a CL + K a C L +
1
2
3
4
pH
pH
pH
pH

+ Ka
+ Ka
+ Ka
+ Ka
10
10
10
10

= [Cu 2 + ]
5
6

K a CL
K a CL

+ 6 pH
+ 5 pH

+ Ka
+ Ka
10
10

[Cu 2 + ] =

1
2

K a CL
K a CL
K a CL
K a CL
+ 2 pH
+ 3 pH
+ 4 pH
+
1 + 1 pH
+ Ka
+ Ka
+ Ka
+ K a
10
10
10
10
5

K a CL
K a CL

+ 6 pH
+ 5 pH
+ K a
+ Ka
10
10

,
0
= red
red

RT
1

+
ln
2
3
4

2 F


1 + 1 K a CL + 2 K a CL + 3 K a CL + 4 K a CL +
10 pH + K
10 pH + K
10 pH + K
10 pH + K

a
a
a
a

5
6

K a CL
K a CL
+ 6 pH

+ 5 pH
+ Ka
+ Ka
10
10

K a = 10 pK a
K n = 10 lg K n

E(Cu2+),V
0,40
0,35
0,30
0,25
0,20
C=0,1mol/L

0,15

C=0,5mol/L
0,10

C=5mol/L

0,05
0,00
0,05
0,10
0,15

pH
0,0

5,0

10,0

www.biosan.lv

Final results of BCC 2011


Nr.p.k.
max
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
33
34
35
36
37
38
39
40

Name
Sigitas Mikutis
Emilis Bruzas
Jurgis Kuliesius
Kristina Smokrovich
Taivo Pungas
Rene Lomp
Jana Volaric
Julia Tseglakova
Mirna Mustapi
Aurimas Narkevicius
Kaur Aare Saar
Mindaugas Siauciulis
Eva-Lotta Kasper
Katrina Sepp
Lona-Liisa Sutt
Jnis Brika
Valdis Dakus
Jaan Toots
Kristers Ozols
Kert Ptsepp
Mantas Vasiliauskas
George Trenin
Ralf Ahi
Mris Serns
Vytaute Maciulsyte
Elza Linia
Kaur Karus
Greta Macileviciute
Ernestas Blazevic
Erik Tamre
Gediminas Aucina
Katrna Krievia
Augustinas Juskauskas
Madis Ollikainen
Tatjana Gerasimova
Pijus Savickas
Simonas Balkaitis
j Svambaryte
y
Silvija
Dovile Meliauskaite
International jury:

State
LT
LT
LT
CR
EE
EE
CR
EE
CR
LT
EE
LT
EE
EE
EE
LV
LV
EE
LV
EE
LT
LV
EE
LV
LT
LV
EE
LT
LT
EE
LT
LV
LT
EE
LV
LT
LT
LT
LT

School

Klaipeda "Azuolynas" gymnasium


Vilniaus irmnu gimnazija
V. gimnazija
Tallinn Secondary Science School
Liivalaia Secondary school
V. gimnazija
Tallinn High School of Humanities
V. gimnazija
KTUG
Tallinn English College
Mykolas Birziska gymnasium
Hugo Treffner Gymnasium
Miina Harma Gumnaasium
Miina Harma Gumnaasium
Salas secondaryy school
Vinu secondary school
Tallinna Reaalkool
Riga State Gymnasium No.3
Tallinn Secondary Science School
Kurnu Lauryno Ivinskio gymnasium
Riga 95th Secondary school
Riga State Gymnasium No.1

Form TOTAL

12
12
12
11
4th
11
4th
11
10
11
11
12
10
11
11
10
11
12
10
10

Riga State Gymnasium No.3

Riga State Gymnasium No.1

11

Riga Secondary school No. 72

12

150,00
107,71
105,83
102,56
97,99
95,53
94,19
93,91
91,05
86,75
82,51
80,82
67,49
64,54
59,94
55,46
,
53,45
50,30
48,88
43,02
35,08
33,86
27,61
23,10
19,25
18,75
17,20
,
13,25
11,01
10,81
8,50
7,40
6,08
6,05
5,52
5,29
5,24
4,26
,
4,14
3,00

Prize
1st place
2nd place
3rd place
Honorary mention
Honorary mention
Honorary mention
Honorary mention
Honorary mention

Egle Maksimaviciute LT
Vladislav Ivanitev EE
Kaspars Veldre LV
Filip Topi CRO

Students will be awarded during Chemistry Olympiad of Baltic states, 2011, April 15-17, Vilnius, Lithuania

1.
8
3,28
6,24
4,64
4,04
5,56
4
3,12
1,28
2,84
2,44
0
0
3,72
3,68
3,16
,
0,8
0
1,08
0
0,12
0,2

2.
10
9,25
9,25
7,75
6,25
9
7
6
8
4,5
6
0
4
8,5
7,75
0,75
,
6,25
0
0
8
9,25
5,25

0
0
0
0
,
1,6
0,24
3,64
0
0
0,84
0,12
0
0,6
0
0,12
0
0,52

4,5
0
6,75
0
0
0,75
0
0
0
0
0
0
0
0
0
0
0

Round 1
3.
4.
4
8
4
7,724
4
8
1
7,724
4
6,345
0
8
4
8
4
8
7,72
0
4
6,621
4
6,345
0
7,034
0
7,448
0
7,172
0
8
0
6,621
,
7,72
0
0
5,793
0
8
4
7,172
0
7,034
0
4,966
0
0
4
0
0
0
0
0
0
0
0
0
0
0
0
0
0

7,172
0
8
0
0
5,517
7,172
0
0
5,241
5,931
5,517
4,69
5,241
4,138
,
4,138
2,483

Sum
30
24,25
27,49
21,11
20,63
22,56
23
21,12
17
17,96
18,78
7,034
11,45
19,39
19,43
10,53
,
14,77
5,793
9,08
19,17
16,4
10,42
0
11,67
0
18,75
0
,
1,6
6,507
10,81
0
0
6,081
6,051
5,517
5,29
5,241
4,258
,
4,138
3,003

1.
5
4,1
3,8
4,5
3,65
5
6
4,25
2,8
3,75
4,3
4
4,15
4,38
4,13
4,45
0
3,5
0
0
4,5
2,6

2.
5
2,32
3
4,5
4,16
3,83
3,205
3,85
4
3,33
3,285
3,58
3,75
2,5
0,83
3,375

4
3,65
0
4,15
,
2,5
3,25
0
0
4,23
0
0
0
0
0
0
0
0

Round 2
3.
4.
10
5
7,5
5
7
4,5
8,9
4,5
9,3
4,5
9,2
5
8,9
5
9,4
5
4
5
8,8
5
7,5
5
8,5
5
6,5
3,5
3
0
4,5
3
5,4
5

5.
5
4,6
3,9
4,8
2,5
2
1,5
2,8
3,8
3,7
1,2
1
1,1
1,2
0,7
2

3,17

3,5

0,4

1,875
1

4,3
0

2,5
1

1
0,9

2,125
3

0,4
8,9

4
3

0,9
0,7

2,045
,
0,25
1,25

6
,
3,9
0

3,5
4
0

1,5
1
0

2,17

7,5
0

0
1

1
0

Sum
30
23,52
22,2
27,2
24,11
25,03
24,605
25,3
19,6
24,58
21,285
22,08
19
11,08
13,16
20,225
0
12,57
0
0
14,175
5,5
0
11,425
19,25
0
17,195
,
11,65
4,5
0
8,5
7,4
0
0
0
0
0
0
0
0

1.
5
3,5
3,5
4
3,5
4

Round 3
3.
4.
8
9
8
5,499
7,002
3,2
6,201
8
6,804
0
1,602
8
8
4,302
3,2
2,196
8
4,725
0
1,305
0
0,801
0
0,504
0
0

3,5
4,5
3,5
3,5
3
3,5
2,5

2.
8
4,83
7,17
3,54
7,17
2,33
0,375
4,08
6,5
5,21
3,17
1,5
1,5
0

1
5

0
0,833

0
0

0,594
0,594

1,5

0,999

Sum
30,00
21,83
17,67
16,94
25,47
7,93
8,38
19,88
16,40
21,44
7,98
5,30
5,50
2,50
0,00
0,00
,
0,00
1,59
6,43
0,00
4,50
0,00
0,00
0,00
0,00
0,00
0,00
,
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
,
0,00
0,00

Part A
30,00
23,50
24,50
22,50
23,00
23,50
25,00
24,00
24,00
22,50
19,50
24,50
22,00
21,50
21,50
20,00
,
21,00
21,50
23,00
19,00
0,00
17,00
21,50
0,00
0,00
0,00
0,00
,
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
,
0,00
0,00

Part B1
8,00
2,35
4,47
2,59
1,41
3,53
3,76
0,00
3,29
0,00
5,88
7,29
0,71
6,82
2,59
4,71
,
8,00
7,29
3,29
3,06
0,94
0,00

FINAL ROUND
Part B2 Part B3
10,00
6,00
6,25
6,00
7,50
6,00
7,78
4,44
0,00
3,36
7,22
5,76
4,17
5,28
3,61
0,00
5,00
5,76
0,28
0,00
5,00
4,08
8,33
5,28
4,03
4,80
0,00
3,24
2,78
0,48
0,00
0,00
,
,
5,83
3,84
0,83
0,72
7,08
0,00
0,83
0,96
0,00
0,00
0,00
0,00
6,11
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
,
,
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
,
,
0,00
0,00
0,00
0,00

Part B4
6,00
0,00
-4,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
1,00
0,00
0,00
0,00
0,00
,
0,00
0,00
0,00
0,00
0,00
0,00

Sum
60,00
38,10
38,47
37,31
27,77
40,01
38,21
27,61
38,05
22,78
34,46
46,41
31,53
31,56
27,35
24,71
,
38,67
30,35
33,38
23,85
0,00
17,94
27,61
0,00
0,00
0,00
0,00
,
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
,
0,00
0,00