2010 U.S.

NATIONAL CHEMISTRY OLYMPIAD

NATIONAL EXAM - PART II
Prepared by the American Chemical Society Olympiad Examinations Task Force

OLYMPIAD EXAMINATIONS TASK FORCE

Arden P. Zipp, Chair, State University of New York, Cortland, NY
James Ayers, Mesa State College, Grand Junction, CO Sherry Berman-Robinson, Consolidated HS, Orlando Park, IL (retired) Seth Brown, University of Notre Dame, Notre Dame, IN Peter Demmin, Amherst HS, Amherst, NY (retired) Marian Dewane, Centennial HS, Boise, ID Xu Duan, Queen Anne School, Upper Marlboro, MD Valerie Ferguson, Moore HS, Moore, OK Julie Furstenau, Thomas B. Doherty HS, Colorado Springs, CO Kimberly Gardner, United States Air Force Academy,CO Regis Goode, Ridge View HS, Columbia, SC Paul Groves, South Pasadena HS, South Pasadena, CA Preston Hayes, Glenbrook South HS, Glenbrook, IL David Hostage, Taft School, Watertown, CT Dennis Kliza, Kincaid School, Houston, TX Adele Mouakad, St. John's School, San Juan, PR Jane Nagurney, Scranton Preparatory School, Scranton, PA Ronald Ragsdale, University of Utah, Salt Lake City, UT
DIRECTIONS TO THE EXAMINER - PART II Part II of this test requires that student answers be written in a response booklet with blank pages. Only this "Blue Book" is graded for a score on Part II. Testing materials, scratch paper, and the "Blue Book" should be made available to the student only during the examination period. All testing materials including scratch paper should be turned in and kept secure until April 26, 2010, after which tests can be returned to students and their teachers for further study. Allow time for the student to read the directions, ask questions, and fill in the required information on the "Blue Book". When the student has completed Part II, or after one hour and forty-five minutes has elapsed, the student must turn in the "Blue Book", Part II of the testing materials, and all scratch paper. Be sure that the student has supplied all of the information requested on the front of the "Blue Book," and that the same identification number used for Part I has been used again for Part II. There are three parts to the National Olympiad Examination. You have the option of administering the three parts in any order, and you are free to schedule rest breaks between parts. Part I 60 questions single-answer multiple-choice 1 hour, 30 minutes Part II 8 questions problem-solving, explanations 1 hour, 45 minutes Part III 2 lab questions laboratory practical 1 hour, 30 minutes A periodic table and other useful information are provided on the back page for student reference. Students should be permitted to use non-programmable calculators. DIRECTIONS TO THE EXAMINEE - PART II DO NOT TURN THE PAGE UNTIL DIRECTED TO DO SO. Part II requires complete responses to questions involving problem-solving and explanations. One hour and forty-five minutes are allowed to complete this part. Be sure to print your name, the name of your school, and your identification number in the spaces provided on the "Blue Book" cover. (Be sure to use the same identification number that was coded onto your Scantron sheet for Part I.) Answer all of the questions in order, and use both sides of the paper. Do not remove the staple. Use separate sheets for scratch paper and do not attach your scratch paper to this examination. When you complete Part II (or at the end of one hour and forty-five minutes) you must turn in all testing materials, scratch paper, and your "Blue Book ". Do not forget to turn in your U.S. citizenship statement before leaving the testing site today. DistributedbyAmericanChemicalSociety,115516thStreet,N.W.,Washington,DC20036 Allrightsreserved.PrintedinU.S.A. PropertyofACSUSNCONotforuseasanUSNCONationalExamafterApril26,2010

amount of substance ampere atmosphere atomic mass unit Avogadro constant Celsius temperature centi prefix coulomb density electromotive force energy of activation enthalpy entropy equilibrium constant

n A atm u NA C c C d E Ea H S K

ABBREVIATIONS AND SYMBOLS Faraday constant F molar mass free energy G mole frequency Plancks constant gas constant R pressure gram g rate constant hour h reaction quotient joule J second kelvin K speed of light kilo prefix k temperature, K liter L time measure of pressure mm Hg vapor pressure milli prefix m volt molal m volume molar M

CONSTANTS M mol h P k Q s c T t VP V V R = 8.314 Jmol1K1 R = 0.0821 Latmmol1K1 1 F = 96,500 Cmol1 1 F = 96,500 JV1mol1 NA = 6.022 1023 mol1 h = 6.626 1034 Js c = 2.998 108 ms1 0 C = 273.15 K

1 1A 1 H
1.008

PERIODIC TABLE OF THE ELEMENTS

2 2A 4 Be
9.012

3 Li
6.941

13 3A 5 B
10.81

14 4A 6 C
12.01

15 5A 7 N
14.01

16 6A 8 O
16.00

17 7A 9 F
19.00

18 8A 2 He
4.003

10 Ne
20.18

11 Na
22.99

12 Mg
24.31

19 K
39.10

20 Ca
40.08

3 3B 21 Sc
44.96

4 4B 22 Ti
47.88

5 5B 23 V
50.94

6 6B 24 Cr
52.00

7 7B 25 Mn
54.94

8 8B 26 Fe
55.85

9 8B 27 Co
58.93

10 8B 28 Ni
58.69

11 1B 29 Cu
63.55

12 2B 30 Zn
65.39

13 Al
26.98

14 Si
28.09

15 P
30.97

16 S
32.07

17 Cl
35.45

18 Ar
39.95

31 Ga
69.72

32 Ge
72.61

33 As
74.92

34 Se
78.96

35 Br
79.90

36 Kr
83.80

37 Rb
85.47

38 Sr
87.62

39 Y
88.91

40 Zr
91.22

41 Nb
92.91

42 Mo
95.94

43 Tc
(98)

44 Ru
101.1

45 Rh
102.9

46 Pd
106.4

47 Ag
107.9

48 Cd
112.4

49 In
114.8

50 Sn
118.7

51 Sb
121.8

52 Te
127.6

53 I
126.9

54 Xe
131.3

55 Cs
132.9

56 Ba
137.3

57 La
138.9

72 Hf
178.5

73 Ta
180.9

74 W
183.8

75 Re
186.2

76 Os
190.2

77 Ir
192.2

78 Pt
195.1

79 Au
197.0

80 Hg
200.6

81 Tl
204.4

82 Pb
207.2

83 Bi
209.0

84 Po
(209)

85 At
(210)

86 Rn
(222)

87 Fr
(223)

88 Ra
(226)

89 Ac
(227)

104 Rf
(261)

105 Db
(262)

106 Sg
(266)

107 Bh
(264)

108 Hs
(277)

109 Mt
(268)

110 Ds
(281)

111 Rg
(272)

112
Uub (277)

113
(Uut)

114
(Uuq)

115
(Uup)

116
(Uuh)

117
(Uus)

118
(Uuo)

58 Ce
140.1

59 Pr
140.9

60 Nd
144.2

61 Pm
(145)

62 Sm
150.4

63 Eu
152.0

64 Gd
157.3

65 Tb
158.9

66 Dy
162.5

67 Ho
164.9

68 Er
167.3

69 Tm
168.9

70 Yb
173.0

71 Lu
175.0

90 Th
232.0

91 Pa
231.0

92 U
238.0

93 Np
(237)

94 Pu
(244)

95 Am
(243)

96 Cm
(247)

97 Bk
(247)

98 Cf
(251)

99 Es
(252)

100 Fm
(257)

101 Md
(258)

102 No
(259)

103 Lr
(262)

Page2

PropertyofACSUSNCONotforuseasanUSNCONationalExamafterApril26,2010

1.

(12%) 5.60 g of solid carbon is placed in a rigid evacuated 2.5 L container. Carbon dioxide is added to the container to a final pressure of 1.50 atm at 298 K. a. Calculate the number of moles of each reactant in the container originally. 2 CO(g) H = 173 kJ b. The container is heated to 1100 K and the following reaction occurs: C(s) + CO2(g) i. Calculate the pressure in the container at this temperature before the reaction takes place. ii. When equilibrium is reached the pressure inside the container is 1.75 times that calculated in b.i. Determine the equilibrium partial pressures of CO2(g) and CO(g). iii. Write the equilibrium expression for this reaction, Kp. iv. Calculate the value of Kp for this reaction at 1100 K. c. Predict the effect on the number of moles of carbon monoxide of each of the following changes made to this system at equilibrium. Give reasons for your predictions. i. The volume of the container is increased to 5.0 L. ii. The pressure inside the container is increased by adding helium. iii. The temperature of the system is increased to 1200 K. iv. The amount of solid carbon is increased to 6.00 g. (14%) Green plants utilize sunlight to convert CO2 and H2O to glucose (C6H12O6) and O2. a. Write a balanced equation for this process. b. Use the information in the accompanying table to calculate i. H ii. S iii. G at 298 K for this reaction. Substance CO2(g) H2O(l) C6H12O6(s) O2(g) Hf kJ/mol 393.5 285.8 1273.3 S J/molK 213.2 69.9 212.1 205.0

2.

c. Comment on the spontaneity of this reaction at 25C and other temperatures. d. Green plants use light with wavelengths near 600 nm for this process. Calculate i. the energy of a 600 nm photon, ii. G for the formation of one molecule of glucose by the reaction in 2a, iii. the minimum number of 600 nm photons required to make one molecule of glucose by the reaction in 2a. e. All of the photosynthesis on earth in a year stores 3.4 1018 kJ of solar energy. i. Use the G for the photosynthetic reaction to calculate the number of moles of CO2 removed from the atmosphere by photosynthesis each year. ii. Determine the mass of carbon that is fixed annually by photosynthesis. 3. (14%) A 0.125 g piece of vanadium reacts with nitric acid to produce 50.0 mL of a yellow solution of vanadium ions in their highest oxidation state. a. Calculate the number of moles of vanadium dissolved and the molarity of vanadium ions in this solution. b. Write the electron configuration of a neutral gaseous vanadium atom. c. Give the oxidation state of vanadium in the yellow solution and outline your reasoning. d. A 25.0 mL portion of this yellow solution is reduced with excess zinc amalgam under an inert atmosphere to give a violet solution. A 10.0 mL aliquot of this violet solution is titrated with a solution of 2.23 10 2 M KMnO4 in acid forming Mn2+. A volume of 13.20 mL of the MnO4 solution is required to convert the vanadium back to yellow. Determine the: i. number of moles of MnO4 used in this titration, ii. mole ratio of vanadium ions to MnO4 ions in this titration, iii. oxidation number change for vanadium in this titration and the oxidation state of vanadium ions in the violet solution. e. When 2.00 mL of the violet solution are mixed with 1.00 mL of the original yellow solution, a green solution results. When this ratio is reversed a bright blue solution is formed. Determine the oxidation states of the green and blue vanadium ions. Support your answers with calculations.

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Page3

4.

(12%) The reaction NO(g) + O3(g) NO2(g) + O2(g) is first order in each reactant with an activation energy, Ea, of 11.7 kJ/mol and a rate constant of k = 1.2 1010 .L mol 1 s 1 at 25 C. a. Calculate the value of the pre-exponential factor, A, in the equation k = Ae Ea/RT. b. Would the A factor for the chemical reaction NO(g) + N2O(g) NO2(g) + N2(g) be expected to be larger or smaller than the A factor in the above reaction if each reaction occurs in a single step? Outline your reasoning. c. Calculate the rate constant for this reaction at 75 C. d. The following two-step mechanism has been proposed for this reaction: Step 1 O3(g) O2(g) + O(g) NO(g) + O(g) NO2(g) Step 2 State and explain whether this mechanism is consistent with the observed rate law.

5. (12%) Write net equations for each of the reactions below. Use appropriate ionic and molecular formulas and omit formulas for all ions or molecules that do not take part in a reaction. Write structural formulas for all organic substances. You need not balance the equations. a. Solutions of hydrochloric acid and silver acetate are mixed. b. A small piece of potassium is added to water. c. Concentrated hydrochloric acid is added to a solution of cobalt(II) sulfate. d. An acidified potassium dichromate solution is added to a tin(II) chloride solution e. Methyl ethanoate (methyl acetate) is reacted with a sodium hydroxide solution. f. Carbon-14 undergoes beta decay. 6. (12%) Account for the following observations on the basis of electrochemical principles. The Standard Reduction Potentials are provided. E = 1.61 V 2 HOCl(aq) + 2 H+(aq) + 2 e Cl2(g) + 2 H2O(l) E = 1.36 V Cl2(g) + 2 e 2 Cl (aq) O2(g) + 4 H+(aq) + 2 e 2 H2O(l) Cu (aq) + 2 e Cu(s)
2+

E = 1.23 V E = 0.34 V E = 0.14 V E = 0.44 V E = 0.76 V

Sn (aq) + 2 e Sn(s)
2+

Fe (aq) + 2 e Fe(s)
2+

Zn (aq) + 2 e Zn(s)
2+

a.

In a voltaic cell made with Cu metal in a 1.0 M CuSO4 and Zn metal in 1.0 M ZnSO4 the Zn is the anode and the cell potential is more than 1.0 V. When aqueous sodium sulfide is added to the CuSO4 solution the cell potential decreases substantially. b. Iron metal corrodes readily in moist air but this corrosion can be prevented when iron is coated with tin or zinc. Corrosion is prevented when the zinc coating is intact or broken. In contrast, corrosion is prevented by coating iron with tin only as long as the tin coating remains intact but actually occurs faster when there is a break in the tin coating. c. In acid solution chloride and hypochlorite ions react to form chlorine gas whereas in basic solution chlorine gas reacts to form chloride and hypochlorite ions.

7. (12%) Two stable allotropes of oxygen are dioxygen (O2) and ozone (O3). a. Describe the geometry of ozone and state the hybridization of each of the oxygen atoms. b. Ozone has a nonzero dipole moment. Account for this fact and predict the direction of the dipole moment. c. Dioxygen is weakly attracted to strong magnetic fields (i.e. is paramagnetic), while ozone is weakly repelled by magnetic fields (i.e. is diamagnetic). Account for these observations in terms of the bonding in the two molecules. d. The most stable allotrope of sulfur is the cyclic S8 molecule while S2 is a highly unstable gas. In contrast, O2 is the most stable allotrope of oxygen and O8 is unknown. Account for these differences in the relative stability of the allotropes of these two elements. 8. (12%) There are four structural isomers with the formula C4H9Cl, one of which exists in optically active forms. a. Write structural formulas for these four isomers. b. Identify the isomer that exists in optically active forms and describe the difference in behavior of these two forms. c. Each of these isomers reacts with OH ions to eliminate a molecule of HCl. i. Give the name and molecular formula for the family of compounds formed by this elimination reaction. ii. Write a structural formula for each of the elimination products. iii. Identify the elimination product that can exist in different isomeric forms and draw structures for these forms. Page4 PropertyofACSUSNCONotforuseasanUSNCONationalExamafterApril26,2010

2010 U.S. NATIONAL CHEMISTRY OLYMPIAD

NATIONAL EXAM - PART II - KEY
1
1mol = .466mol 12.01g CO2 n = PV RT n = (1.50atm )(2.5L ) / 298K (.0821) n = 0.153mol (1100K ) P2 = 5.54atm b. (i). P2 = P1 T2 / T1 P2 = 1.50atm 298K (9.70atm)(2.5L) n = PV RT (ii). PT = 1.75(5.54) = 9.70atm n= = 0.268mol 1100K (.0821) 0.268 = 0.153 x + 2x x = 0.268 0.153 x = .115 nRT (.038)(.0821)1100 = 1.3atm n CO = 0.230 PCO 2 = PCO 2 = n CO 2 = 0.038 V 2.5L (.230)(.0821)1100 PCO = 8.31atm PCO = = 8.31atm 2.5L (.0821)(1100) 9.70atm = (0.153 x ) + 2x 0.269 = 0.153 + x x = .116 2 .5

a. 5.60gC

(iii). K p =

PCO 2

PCO 2
2

K p = 50.4 1.37 c. (i). nCO will increase. As V is , P s so system shifts . (ii). nCO does not change. He is not in K p so has no effect.

(iv). K p = (8.31)

(iii). nCO will increase.. is positive so T will favor . (iv). nCO will not change. Solids do not affect equilibrium. 2 a. 6CO2+6H2O C6H12O6+6O2 b. (i). H = 1273.3+0[6(393.5)+6(285.8)] = 1273.3[23611714.8] = 1273.3+4075.8 = 2802.5 kJ (ii). S = 212.1+6(205.0)[6(213.2+6(69.9) = 212.1+1230.0[1279.2+419.4] = 1442.11698.6 = 256.5 J/mol K (iii). G = HTS G = 2802.5 kJ298(.2565 kJ/mol) G = 2802.5 kJ+76.44 = 2878.9 kJ/mol c. Reaction is not spontaneous at 25C because G>0 Reaction is not spontaneous at other Ts because H>0 and S<0 d. (i). = h c = = hc
(6.626 10 34 )(3 108 ) 600 10 9 E = 3.31 10 19 J kJ 1mol = 4.78 10 21 kJ mol ec = 4.78 10 18 J molec (ii). G o / molecule = 2878.9 mol 6.022 10 23 molec J 1phot = 14.4photons (iii). # of photons = 4.78 10 18 molec 3.31 10 19 J 1molC6 H12 O 6 6molCO 2 e. (i). 3.4 1018 kJ yr = 7.08 1015 molCO 2 2.88 103 kJ 1molC6 H12 O 6 E=

(ii). 7.08 1015 molC 12.01 g mol = 8.50 1016 gC

1mol = .00245mol 50.94g .00245mol M= = 0.049M .050L b. V Z = 23 1s2 2s2 2p6 3s2 3p6 4s2 3d 3 c. V is in +5 oxid st. due to loss of 4s and 3d electrons. d. (i). mol MnO 4 = 2.23 10 2 mol L .01320L = 2.94 10 4 mol

a. 0.125gV

(0.010L)(.0491 mol L) 4.91 10 4 1.67 = = 1 2.94 10 4 mol 2.94 10 4 5 1.67 = 3.0 for V (iii). Mn goes from +7 +2 = 5

(ii).

V 2 + violet x = 3 green
x = 4 blue

e. 2.00( x 2) = 1.00(5 x ) 1.00( x 2) = 2.00(5 x ) 4 a. k = e

Ea RT

2x 4 = 5 x x 2 = 10 2x

3x = 9 3x = 12

1.2 1010 = e 8.11700 J ) 314 ( 298

1.2 1010 = e 4.722

= 1.2 1010 / .008894 = 1.35 1012 b. The A factor for NO and N2O would be smaller than that for NO and O3 because there are fewer geometric arrangements involving NO and N2O molecules that could lead to a successful reaction. The probability of successful reactions are lower for NO and N2O. E 1 k 1 c. ln 2 = a T T k1 R 1 2

ln

k2 11700J 1 1 = 10 J 298 348 1.2 10 8.314 MolK = 1407.3(.0033557 .0028736 )

k2 1.2 1010
= 1407.3 4.821 10 4 k2 = 0.6785 = 1.971 1.2 1010

ln

k 2 = 2.37 1010

d. This mechanism would give either R = k[O 3 ] if first step is the slow one or R = k

[ NO][O 3 ] if second step [O 2 ]

is slow since neither of these rate laws R = k[ NO][O 3 ] this cant be the mechanism. 5
a. H + + Cl + Ag + + C 2 H 3O 2 AgCl + HC 2 H 3O 2

b. K + H 2 O K + + OH + H 2 c. H + + Cl + Co 2 + + SO 2 CoCl 2 + HSO 4 4 4
2 d. Cr2 O 7 + H + + Sn 2+ Cr 3+ + Sn 4+ + H 2 O

e.

H3CCOCH3 + OH- H 3CCO -

+ H3COH

f. 6

14 14 0 6 C 7 N + 1

E cell = 0.76 + 0.34 = 1.08V a. Zn + Cu2+ Zn2+ + Cu 22+ When S is added to Cu /Cu half cell CuS forms reducing [Cu2+], shifting the reaction to the left and decreasing Ecell b. Fe Fe2+ +2e is 0.44V so oxidation (corrosion) is spontaneous. Covering surface with Sn or Zn prevents reaction with O2. If Zn coating is broken, Zn will still oxidize preferential. If Sn coating is broken, Fe will oxidize more readily c. 2HOCl + 2H+ + 2Cl 2Cl2 + 2H2O o = 0.25 spontaneous in acid. + In basic solution [H ] is very low so reaction shifts to the left and Cl2 forms Cl and OCl.

a.

O
2

O3 is bent. Central O is Sp hybridized. All 3 are Sp hybridized in delocalized structure. b. Formal charge for central O is +1, for each of terminal Os in delocalized structure. (-1 and O in each resonance form). DM has + end on central O. c. O3 is diamagnetic because all e are paired. O2 is paramagnetic because it has 2 unpaired e (M.O theory). K 4 2 *2 2 p 2 p *2 *1*1 2s 2 2 d. P orbitals overlap better in smaller O atoms. So double bond in O2 is stronger that 2 single bonds / e-e repulsion between O atoms weakens single bonds. S is larger than O so p orbitals dont overlap as well S-S . Double bond is weaker that 2 single bonds. S-S bonds are longer so e-e repulsion is lower. 8 a.
C C C C Cl
C C Cl C C
C Cl C CH 3 C

C CH 3

Cl

b.
C C

Cl C C

Occurs in optically active forms.

Cl C 2 H5 C H CH 3 Cl

Vs

CH3

C H

C2 H 5

They differ in the direction they rotate plane polarized light. c. (i). Alkenes C4H8. (ii).
C
C C C C C C C C

(iii).
C C C C

Exists in isomeric forms

CH 3 C H C H CH 3

CH 3

C C C CH3

and
H