41th Latvian National Chemistry Olympiad (2000) Theoretical problems

Honourable olympian!
Organizing comitee of the 41th Latvian National Chemistry Olympiad congratulates you with success in preliminary round and wishes good luck in the final round! To provide oppurtunity for each participant completely demonstrate his knowledge in chemistry and its boundaries we offer quite large number of problems. To achieve the best result and not lose points because of misunderstanding or laxity read carefuly these instructions before start with solving problems! 1. Every participant receives a complete set of all problems with 32 problems and a test with 7 questions different for each class. 2. After the index number of problem there are indicated classes wich should solve it. If more than one class is indicated all should solve the problem. There are 9 problems and a test for each participant. 3. Participants from younger classes may solve problems of elder. Example. 13. 4. This problem is for classes 10 and 11 participants from class 9 also may solve it while those from class 12 may not. 5. Behind classes the maximal number of points for the problem is indicated. If there is added + or +x there is a chance to get extra points answering the extra questions in the problem beginnig with "if you can ...". 6. If you have any questions regarding the problems be sure to ask the responsible person from organizing comitee who is present during the theoretical examination. Mutual consultations between participants are not allowed. 7. After complete or partial solving of a problem escribe the respective number on your participant's card and cross the numbers wich you didn't try to solve. This eases the job of estimators and will prevent potential misunderstandings. Good luck! Preparatory problems, results and other information you can find on our web page: http://www.liis.lv/chem/! 10-11 5+x p.

1.

8 p.

Write down the equations for each reaction of the following chain! Na NaOH NaCl HCl ZnCl2 ZnSO4 Zn(OH)2 Zn(NO3)2 2. 9 5 p.

ZnO

150 g 12% Cr2(SO4)3 solution was addedCr2(SO4)3.15H2O until part of Cr2(SO4)3 in solutions becomes 30%. Calculate the mass of Cr2(SO4)3.15H2O added to solution! 3. 9 8 p.

The chemical formula of mineral selenite could be written: CaSO4xX. Experimentaly is established that selenite contains 23,3 % calcium, 18,6 % sulphur, 55,8 % oxygen and one more element. What is chemical formula of selenite! How much of selenium contains selenite? 4. 9 13 p.

Limestone usually contains a bit of sand. To determine the mass part of calcium carbonate in limestone a sample weighting 0.1327 g is treated with 10.00 ml of hydrochloric acid wih concentration 0.4555 mol/l. The excess of hydrochloric acid is neutralized with 20.41 ml of sodium hydroxide (0.1001 mol/l). a) Calculate the mass part of calcium carbonate in the limestone. Uncleared lime was obtained from the given limestone however calcium carbonate was not completely resolved. To determine the part of calcium carbonate resolved a sample of uncleared lime (0.1111 g) was treated with 10.00 ml of hydrochloric acid (0.4993 mol/l). Excess of hydrochloric acid was neutralized with 14.24 ml of sodium hydroxide (0.1001 mol/l). b) Calculate the composition of the uncleared lime. 5. 9 6 p.

In cookery to make duff looser ammonium hydrogencarbonate is used. Write down the equations to obtain the compound only from carbon, air and water. 6. 9 5 p.

Group the oxides according to the conditions 1.-4. CaO , SiO2 , SO2 , MgO , Fe2O3 , SO3 , BaO , P2O5 1. Oxides form acids when reacting with water 2. Oxides form bases when reacting with water 3. Oxides form alkali when reacting with water

4. Oxides doesn't react with water In cases when reaction occurs write the appriate equation! 7. 9 11 p.

While solving in water 3.60 g of a white crystalline substance A, occured 3.36 l of hydrogen gas. While solving in water 4.21 g of a similar white crystalline substance B, occurs 4.48 l of hydrogen gas. Said that in the beginning of the 20th Century compound B was used for military purposes. 1. Name substances A and B! 2. Write the equations the reactions occoured! 3. Can you say for what purpose substance B was used during World War One? 8. 9 8 p.

By long heating of magnesium carbonate hydrate its mass decreased 4.4 times. Determine the formula of magnesium carbonate hydrate and write the equations for chemical reactions. 9. 9-10 6 p.

On 17,6 grams of sodium chloride was poured excess of conc. sulfuric acid and the evolved gas was introduced in 106 g of 20.0% sodium carbonate solution. Wheather the obtained solution will be acidic or alkaline? 10. 10 8 p.

Write down the equations for each reaction of the following chain! CO2 Na2CO3 NaHCO3 Na2SO4 NaBr NaNO3 HNO3 Fe(OH)3 11. 10 5 p.

Fe(NO3)3

Fishermen catched plaices and brought them home. Some fisherman usher them in a bath filled with fresh water, after some time the plaices became much bolder. Why? What should the fisherman do to let plaices live in the bath? 12. 10 6 p.

Nowdays a modern and widely used method of analyses is masspectrography wich is based on sorting the particles according to their mass. Air was analysed with a masspectrometer. The obtained masspectrum is shown in the picture. Solve the spectrum pointing coumpounds related to the peaks in the spectrum.

M, g/mol 13. 10 6 p.

When protractedly holded in the air water obtained from an underground water source usually occurs brown precipitation of iron(iii) hydroxide although instantly obtained underground water usually doesn't contain Fe3+ ions. How is this to be explained? 14. 10 6 p.

100 ml of water in 20C was saturated with ammonia and in this solution carbon dioxide was introduced until the composition of the solution became constant. Occured 160 g of precipitation. Calculate the composition of the solution after the introduction of carbon dioxide. The solubility of carbon dioxide should be discounted. In 20C temperature solubility of ammonia in water is 52.6 l in 100 l of water. 15. 10 5 p.

In thermal power stations it's important to prevent incrustation in boilers. The hardness of water is eliminated using ionits - balls of polymer containing SO3H groups. Hydrogen atoms in these groups are able to exchange with calcium or magnesium ions: calcium and magnesium ions remain bounded to the polymer. Calculate mass for ionite needed to soften 1,0 m3 water with total hardness 3,0 mmol/l. 1,0 g of ionite contains 10 mmol SO3H groups. 16. 10 5 p.

In the water of a salt lake mainly sodium chloride is found during summer it crystallizes. However in winter crystallization of another compound may occur and the formed precipitation can last even until the next summer. From 1.00 tonn of this compound one

may obtain to 619 kg of common salt. What is this compound and how can one obtain common salt from it? 17. 10-11 6 p.

It's certain that gaseous NO2 molecules in low temperatures dimerize. Explain why a similar process doesn't occour with molecules of SO2 . 18. 11 8 p.

Write down the equations for each reaction of the following chain! CaCO3 CaO CaCl2 CaSO4 CaS CaCl2 Ca3PO4 Ca3P2 19. 11 8 p.

PH3

To 0.500 litres of BaCl2 solution whose osmotic pressure at 200C is 14.6 kPa was added 0.500 litres Na2SO4 with the same osmotic pressure. Calculate quantity of substances in the given solutions as well as in the obatained and the osmotic pressure of the obtained solution. 20. 11 5 p.

Especially comfortable way to verify when the distilled water has actually been distilled is to determine its pH. If pH is near to 7.0 then the water is distilled in the same day If pH is in the interval 5.56.0 the water is distilled some days ago. Explain the sense of this test if necessary write down equations for appropriate reactions. 21. 11 8 p.

To 200,0 g of 24,34% FeCl3 solution was added 16.35 g of zink powder and then the bowl was closed. Substances in the solution reacted. After the reaction to a sample of the solution potassium rodanide was added. The solution didn't became red. When solution of ammonia was added to another sample precipitation formed. By adding more ammonia the ammount of precipitation decreased. Calculate the composition of the solution after the reaction. 22. 11 11 p.

In separate bowls 3,100 g Pb(NO3)2 and 1,580 g KMnO4 was heated and the formed gases were introduced in 1 litre of water. In the same water also was introduced a gas formed

while 1,008 g of Na2SO3 reacting with excess of sulfuric acid. To what volume should the obtained solution be diluted for its pH to become 4. 23. 11 15 p.

Colourless substance A doesn't react with oxygen nor in the room temperature nor in elevated temperature however it: 1. exothermicaly reacts with a silver-white metal B by forming the only one product of the reaction D whose mass is 1.66 times that of B; 2. above 800 oC reacts with colourless very hard substance C forming a gaseous product E whose mass is 3.67 times that of C; In atmosphere of E heated metal B burns forming D and a dark fine powder F whose chemical composition is the same as that of C. What are compounds A-F? Write equations of the chemical reactions noted. 24. 11-12 14 p.

In 1748 the city of Pompei buried by volcano in 79 AD was digged out. Among the plenty of findings a fragment of the Roman waterpipe was obtained which was coated by a dense yellowish oxide. To find out what was the waterpipe made of chemists acted as follows: weighted 2.00 grams of the waterpipe's fragment (metal with the oxide) and then dropped drop by drop 50.0 % acetic acid (univalent acid, HA) solution ( = 1,06 g/ ml, MHA = 60,1 g/ mol) until the sample was competely dissolved. They needed 2.17 ml of acetic acid for it. Determine what metal the waterpipe was made of. Explain the choice of the ancient Romans. 25. 11-12 8 p.

The very top of the Monument of Freedom - Mother Latvia is covered with basical copper(ii) carbonate (CuOH)2CO3 or Cu(OH)2xCuCO3 layer. This compound is water insoluble but as one can see in the upper part of the Monument's column a part of Cu(OH)2xCuCO3 from the head of the Monument has shifted down the colmun because of rain (see the picture). Try to explain how the insoluble basical copper carbonate can be

shifted down by rain.

26.

12

8 p.

Write down the equations for each reaction of the following chain! C2H5OH MnCO3 27. 12 CH3COOH Mn(NO3)2 CH3COOCH3 CH3OH CH3OCH3 CO2 K2CO3

6 p.

When 1,00 l of cis-2-butene and trans-2-butene mixture was hydrogenated evolved 5.18 kJ of heat. Calculate composition of the mixture. Heat of hydrogenation of cis-2-butene is 119.0 kJ/mol and that of trans-2-butene - 114.6 kJ/mol. 28. 12 11 p.

Already since 1872 problem of so called acidic rains is actual. Acidic atmospherical falls decrease pH of the lakes seriously affecting biological processes. When decreases pH of the lakes begins disolving of aluminium hydroxide what simplifying could be written: Al3+ + 2H2O Al(OH)2+ + H3O+; 2+ Al(OH) + 2H2O Al(OH)2+ + H3O+; Al(OH)2+ + 2H2O Al(OH)3 + H3O+; In the last time it's proved that exactly the soluble aluminium compounds (Al3+, Al(OH)2+, Al(OH)2+) are one of the main factors determining the toxical effect of the acidification of the environment because the soluble compounds much easily can get into organisms of various living beings. Supposing that aluminium in lake is only in form of Al3+, Al(OH)2+, Al(OH)2+ and Al(OH)3

calculate what part (in molar %) of aluminium compounds are in insoluble Al(OH)3 form in the following lakes:

Vertage lake, lake's water's pH = 5,0 Chortock, lake's water's pH = 6,4

Aluminium hydrocomplexes' stability constants: ; ; ; K1 = 109,0; K2 = 1017,9; K3 = 1025,2 Make conclusions about the lake's pH influence on Al compounds solubility. In wich lake you predict the less toxical action of aluminium compounds. 29. 12 6 p.

In a reaction of some gaseous alkane with a gaseous halogen formed a gaseous compound wich contains 86.4% of halogen. Write the equation for this reaction. 30. 12 6 p.

Finish the chemical equations! CH3CH2Cl + KOH + KCl + KOH C2H4 + + + CH3CH2OCH2CH3 + KCl 31. 12 13 p.

In elemental analyses of a colourless substance X was established that it contains 65.5% C, 5.46% H and oxygen. Compound X is a weak acid; 0.10 g of X in a solution completely reacted with 18.2 ml 0.10 mol/l Sodium hydroxide (indicator - phenolftalein)[reaction 1]. Product of this reaction - compound Y: 1. in a cold alkaline solution reacts with acetylchloride (CH3COCl)(in excess) forming Q [reaction 2]; 2. reacts with iodomethane (in excess) forming Z [reaction 3]; 3. protractedly holded in air this solution becomes yellow and later - brown. Besides compound X reacts with silver oxide in ammonia (silver mirror reaction) [recation 4] to form yellow compound A. But in a neutral medium it gives blue colour when treated with diluted FeCl3 solution. What's compounds X, Y, Z, Q, A? Write equations for reactions 1 - 4. What purposes is compound X used for in praxis? Wich of the described reactions is basis for practical applications of X?

32.

12

10 p.

A and B are gases which easily react with benzene in presence of aluminium chloride. In sunlight they react mutually and depending on stochiometry three liquid compounds may form. One of its is charachterized by sweetish odour and it was uesed for narcosis in the beginning of the 20th century. Write equations for all reactions. Explain why in one case forming of C and C' is likely whereas in other - not.

Good luck!

41th Latvian National Chemistry Olympiad (2000) Theoretical answers

Only the most complex equatations: 2 Zn(NO3)2 2. 9 2 ZnO + 4NO2 + O2 5 p.

m(Cr2(SO4)3.15H2O)=295g 3. 9 8 p.

Selenite : CaSO4.H4O2 or CaSO4. 2H2O. As there is no selenium in selenite , it contains 0,00 % of selenium. 4. 9 13 p.

a) w(CaCO3) = 0,9465. w(SiO2) = 1 w(CaCO3) = 0,0535. b) m(CaO) = 0,07471 g, w(CaO) = 67,2%; m(CaCO3) = 0,02332 g, w(CaCO3) = 21,0%; m(SiO2) = 0,0131 g; w(SiO2) = 11,8%. 5. 9 6 p. CO + H2

C + O2 CO2 H2O + C 2 N2 + 3 H 2 2 NH3 NH3 + CO2 + H2O NH4HCO3 7. 9 11 p.

A - NaH, B - CaH2 . NaH + H2O = NaOH + H2 CaH2 + 2H2O = Ca(OH)2 + 2H2

8.

8 p.

Magnesium carbonate pentahydrate was heated - MgCO3.5H2O. 9. 9-10 6 p.

As the solution contains NaHCO3 pH > 7 . 10. 10 8 p. NaHCO3 Na2SO4 NaBr NaNO3 HNO3 Fe(NO3)3

CO2 Na2CO3 Fe(OH)3

Only the most complex equtations: Na2SO4 + BaBr2 BaSO4 + NaBr NaBr + AgNO3 AgBr + NaNO3 6 HNO3 + Fe Fe(NO3)3 + 3 NO2 + 3H2O 11. 10 5 p.

Fisherman should have placed the plaices in a salty water. 12. 10 6 p.

H2O (18), N2 (28), O2 (32), Ar (40), CO2 (44). 13. 10 6 p. 2Fe3+ + 4OHFe2+ Fe3+ + eO2 + 2H2O + 2e- 4OH-

2Fe2+ + O2 + 2H2O

Fe3+ + 3OH14. 10

Fe(OH)3 6 p.

w(NH4HCO3) = 0,176. 15. 10 5 p.

mj = (nCa + nMg)/cM(-SO3H) = 1000*3,0*10-3/(10*10-3) = 300 g.

16.

10

6 p.

The unknown compound is NaCl*2H2O. NaCl can be obtained by heating in the sun. 17. 10-11 6 p.

18.

11 CaO

8 p. CaCl2 CaSO4 CaS CaCl2 Ca3PO4 Ca3P2 PH3

CaCO3

Only the most complex equatations: CaSO4 + C CaS + 4 CO or CaSO4 + BaS CaS + BaSO4 Ca3PO4 + 8 C Ca3P2 + 8 CO Ca3P2 + 6 HCl 3 CaCl2 + 2 PH3 19. 11 8 p.

Given solutions contain 0,001mol BaCl2 and 0,001mol Na2SO4, the obtained solution contains 0,002mol NaCl osmotic pressure of the obtained solution - 9,74 kPa 20. 11 5 p. CO2 (s) HCO3- + H3O+ CO32- + H3O+ 8 p.

CO2 (g) + H2O CO2 (s) + 2H2O HCO3- + 2H2O 21. 11

After the reaction the solution contains 16,2% of ZnCl2 and 12,0% of FeCl2

22.

11

11 p.

The obtained mixture of acids should be diluted to 347 litres. 23. 11 15 p.

A O2 B Mg C - C (diamond) D MgO E CO2 F C (graphite) 24. 11-12 14 p.

The waterpipe was made of lead. 25. 11-12 8 p.

SO2 + 2H2O HSO3- + H3O+ CO2 + 2H2O HCO3- + H3O+ Cu(OH)2 + 2H3O+ Cu2+ + 4H2O CuCO3 + 2H3O+ Cu2+ + 3H2O + CO2 CO2 + 3H2O CO32- + 2H3O+ 2Cu2+ + CO32- + 4H2O Cu(OH)2. CuCO3 + 2H3O+ H3O+ + CO32HCO3- + H2O 26. 12 CH3COOH Mn(NO3)2 8 p. CH3COOCH3 CH3OH CH3OCH3 CO2 K2CO3

C2H5OH MnCO3

Reagents: 1. CrO3 (or dichromates), KMnO4; 2. CH3OH, H+ 3. OH4. CH3ONa 5. O2 (combustion) 6. KOH 7. MnCl2 8. dil. HNO3

27.

12

6 p.

119,0*ncis + 114,6*ntrans = 5,18 ncis + ntrans = 1/22,4 ncis = 0,0145 mol, ntrans = 0,0301 mol; cis = 32,5%, trans = 67,5%. 28. 12 11 p.

Lake Vertage [Al(OH)3] = 0,002 % Lake Chortock [Al(OH)3] = 32 % 29. 12 6 p. CnH2n+2-aFa + a HF

If halogen is fluorine: CnH2n+2 + a F2 n = 1, a = 4. If halogen is chlorine

n = 1, a = 2,86; n = 2, a = 5,37; n = 3, a = 7,87 As chloropropanes are liquids the only matching reaction is CH4 + 4 F2 30. 12 6 p.

CF4 + 4 HF.

CH3CH2Cl + KOH CH3CH2OH + KCl CH3CH2Cl + KOH C2H4 + KCl + H2O CH3CH2Cl + CH3CH2OK CH3CH2OCH2CH3 + KCl 31. 12 13 p.

[1] C6H4 (OH)2 + 2 NaOH C6H4 (ONa)2 + 2 H2O [2] C6H4 (ONa)2 + CH3COCl C6H4 (OCOCH3)2 + 2NaCl [3] C6H4 (ONa)2 + CH3I C6H4 (OCH3)2 + 2NaI

[4]

X 1,4-dihydroxylbenzene (hydrohinone); Y X sodium salt; Z 1,4-dimetoxybenzene; Q 1,4-diacetylbenzene; A 1,4-benzohinone 32. 12 10 p.