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1999 U. S.

NATIONAL
CHEMISTRY OLYMPIAD
NATIONAL EXAMPART I
Prepared by the American Chemical Society Olympiad Examinations Task Force

OLYMPIAD EXAMINATIONS TASK FORCE


Arden P. Zipp, State University of New York, Cortland
Chair
James S. Bock, Gateway High School, PA
Edward DeVillafranca (retired), Kent School, CT
Peter E. Demmin (retired), Amherst Central High School, NY
John Krikau, American Chemical Society, DC
Patricia A. Metz, University of Georgia, GA
Ronald O. Ragsdale, University of Utah, UT
Helen M. Stone (retired), Ben L. Smith High School, NC
Diane D. Wolff, Ferrum College, VA

DIRECTIONS TO THE EXAMINERPART I


Part I of this test is designed to be taken with a Scantron answer sheet on which the student records his or her responses. Only this
Scantron sheet is graded for a score on Part I. Testing materials, scratch paper, and the Scantron sheet 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, 1999, 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 requested information on the Scantron sheet. The answer
sheet must be completed using a pencil, not pen. When the student has completed Part I, or after one hour and thirty minutes has
elapsed, the student must turn in the Scantron sheet, Part I of the testing materials, and all scratch paper.
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 questions laboratory practical 1 hour, 15 minutes
A periodic table and other useful information are provided on page 2 for student reference. Students should be permitted to use non-
programmable calculators.

DIRECTIONS TO THE EXAMINEEPART I

DO NOT TURN THE PAGE UNTIL DIRECTED TO DO SO. Answers to questions in Part I must be entered on a Scantron
answer sheet to be scored. Be sure to write you name on the answer sheet; an ID number is already entered for you. Make a record of
this ID number as you will use the same number on both Parts II and III. Each item in Part I consists of a question or an
incomplete statement which is followed by four possible choices. Select the single choice that best answers the question or completes
the statement. Then use a pencil to blacken the space on your answer sheet having the same letter as your choice. You may write on
the examination, but the test booklet will not be used for grading. Scores are based on the number of correct responses. When you
complete Part I (or at the end of one hour and 30 minutes), you must turn in all testing materials, scratch paper, and your Scantron
answer sheet. Do not forget to turn in your U.S. citizenship statement before leaving the testing site today.

Not valid for use as an USNCO National Exam after April 26, 1999.
Distributed by the ACS DivCHED Examinations Institute, Clemson University, Clemson, SC. All rights reserved. Printed in U.S.A.
ABBREVIATIONS AND SYMBOLS CONSTANTS
amount of substance n equilibrium constant K milli- prefix m
ampere A Faraday constant F molal m R = 8.314 Jmol 1K1
atmosphere atm formula molar mass M molar M R = 0.0821 Latmmol 1K1
atomic mass unit u free energy G mole mol 1 F = 96,500 Cmol1
atomic molar mass A frequency Plancks constant h
1 F = 96,500 JV1mol1
Avogadro constant N A gas constant R pressure P
Celsius temperature C gram g rate constant k N A = 6.022 1023 mol1
centi- prefix c hour h second s h = 6.626 1034 Js
coulomb C joule J speed of light c c = 2.998 108 ms1
electromotive force E kelvin K temperature, K T
energy of activation Ea kilo- prefix k time t
enthalpy H liter L volt V
entropy S measure of pressure mmHg volume V

PERIODIC TABLE OF THE ELEMENTS


1 2
H He
1.008 4.003
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.99 24.31 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.61 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 181.0 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 (209) (210) (222)
87 88 89 104 105 106 107 108 109 110 111 112 114
Fr Ra Ac Rf Db Sg Bh Hs Mt
(223) 226.0 227.0 (261) (262) (263) (262) (265) (266) (269) (272) (277) (289)

58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.1 140.9 144.2 (145) 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 231.0 238.0 237.0 (244) (243) (247) (247) (251) (252) (257) (258) (259) (260)

Page 2 Not valid for use as a USNCO National Exam after April 26, 1999
DIRECTIONS
When you have selected your answer to each question, blacken the corresponding space on the answer sheet using a soft, #2
pencil. Make a heavy, full mark, but no stray marks. If you decide to change an answer, erase the unwanted mark very carefully.
Make no marks on the test booklet. Do all calculations on scratch paper provided by your instructor.
There is only one correct answer to each question. Any questions for which more than one response has been blackened will not
be counted.
Your score is based solely on the number of questions you answer correctly. It is to your advantage to answer every question.

1. Which substance is most likely to be soluble in a 6. A 20.00 mL sample of a Ba(OH)2 solution is titrated with
nonpolar solvent? 0.245 M HCl. If 27.15 mL of HCl is required, what is the
molarity of the Ba(OH)2 solution?
(A) glucose (B) graphite
(A) 0.166 M (B) 0.180 M
(C) lithium fluoride (D) sulfur
(C) 0.333 M (D) 0.666 M

2. A solution of which substance can best be used as both a


titrant and its own indicator in an oxidationreduction 7. When ionic hydrides react with water, the products are
titration?
(A) acidic solutions and hydrogen gas.
(A) I2 (B) NaOCl
(B) acidic solutions and oxygen gas.
(C) K2Cr2O7 (D) KMnO4
(C) basic solutions and hydrogen gas.
(D) basic solutions and oxygen gas.
3. What value of
T should be 36
used for the 8. 0.250 g of an element, M, reacts with excess fluorine to
calorimetry 32 produce 0.547 g of the hexafluoride, MF6. What is the
T, C

experiment that element?


gives these 28
graphed results? (A) Cr (B) Mo (C) S (D) Te
24

20 9. How many moles of Na + ions are in 20 mL of 0.40 M


0 2 4 6 8 10 12 14 16 18 20 Na 3PO4?
time, min
(A) 0.0080 (B) 0.024
(A) 10 C (B) 12 C (C) 15 C (D) 19 C (C) 0.050 (D) 0.20

4. Fe3+(aq) + SCN(aq) FeSCN2+(aq) 10. What is the mass Molar Mass, M


percent of oxygen in
The equilibrium constant for this reaction can best be Al2(SO4)318H2O 666.43 gmol
Al2(SO4)318H2O?
determined by means of
(A) chromatography. (B) conductance. (A) 9.60 (B) 28.8 (C) 43.2 (D) 72.0

(C) ion exchange. (D) spectrophotometry.


11. What is the coefficient for H +(aq) when the equation is
balanced with whole number coefficients?
5. Which solid reacts with dilute hydrochloric acid at 25 C
to produce a gas that is more dense than air? __Mn2+(aq) + __BiO3(aq) + __H+(aq)
__Bi3+(aq) + __MnO4(aq) + __H2O(l)
(A) Zn (B) Pb(NO3)2
(A) 3 (B) 4 (C) 7 (D) 14
(C) NaBr (D) NaHCO3

Not valid for use as an USNCO National Examination after April 26, 1999 Page 3
12. What is the number of O2 molecules in the 2.5 g of O 2 19. What is the change in internal energy, E, for a reaction
inhaled by the average person in one minute? that gives off 65 joules of heat and does 38 joules of
work?
(A) 1.9 1022 (B) 3.8 1022
(A) 103 J (B) 27 J (C) +27 J (D) +103 J
(C) 4.7 1022 (D) 9.4 1022

20. What are the signs of H and S for this reaction?


13. Which point in the B
phase diagram best
A 2C (s) + O2(g) 2CO(g)
represents H S
C
P, atm
supercritical
conditions? (A)
D
(B) +
T, C (C) + +
(A) A (B) B (C) C (D) D (D) +

14. The vapor pressure of a liquid in a closed container 21. The rate of formation of O3(g) is 2.0 107 molL1s1 for
depends on the reaction
1. temperature of the liquid 3O2(g) 2O3(g)
2. quantity of liquid What is the rate of disappearance of O2(g) in molL1s1?
3. surface area of the liquid
(A) 1.3 107 (B) 2.0 107
(A) 1 only (B) 2 only
(C) 3.0 107 (D) 4.5 107
(C) 1 and 3 only (D) 1, 2 and 3

22. Which statements are true?


15. What is the maximum number of phases that can be in 1. S values for all elements in their standard states
equilibrium in a one component system? are positive.
2. S values for all aqueous ions are positive.
(A) 1 (B) 2 (C) 3 (D) 4
3. S values for all spontaneous reactions are
positive.
16. The molar mass of a gas with a density of 5.8 gL1 at (A) 1 only (B) 1 and 2 only
25 C and 740 mm Hg is closest to
(C) 2 and 3 only (D) 1, 2 and 3
(A) 10 gmol1 (B) 20 gmol1
(C) 150 gmol1 (D) 190 gmol1
23. Ag+(aq) + 2 NH3(aq) Ag(NH3)2+(aq)
For this reaction, K = 1.7 107 at 25 C. What is the
17. Which substance would be expected to exhibit the value of G in kJ?
greatest surface tension at 25 C?
(A) 41.2 (B) 17.9 (C) +17.9 (D) +41.2
(A) CH3OCH3 (B) C 2H5OH
(C) CH3CH(OH)CH3 (D) CH2(OH)CH2OH
24. The value of H for a reaction can be found by
appropriate combination of bond enthalpies (the energy
18. 3N2O(g) + 2NH3(g) 4N2(g) + 3H2O(g) H = 879.6 kJ required to break a particular bond, represented BE).
Which expression will give H for this reaction?
What is Hf for N2O in Heats of Formation C 2H4(g) + H2(g) C2H6(g)
kJmol1?
NH3 45.9 kJmol1
(A) BEC=C + BEHH [BECC + 2BECH]
H2O 241.8 kJmol1
(B) BECC + 2BECH [BEC=C + BEHH]
(A) +246 (B) +82 (C) 82 (D) 246
(C) 1 /2BEC=C + BEHH 2BECH
(D) 2BECH 1/2BEC=C + BEHH

Page 4 Not valid for use as an USNCO National Examination after April 26, 1999
25. What is the sign of G and the value of K for an 31. P 4(s) + 6Cl2(g) 4PCl 3(g)
o
electrochemical cell for which Ecell = 0.80 V?
Phosphorus reacts with chlorine as shown. What is the
G K equilibrium constant expression, K p, for this reaction?
(A) >1 (A) 4 PPCl 3
(B) 4 PPCl3
6 PPCl PCl 6 PCl2
(B) + >1
3 2

(C) PPCl3 (D) 4


PPCl
(C) + <1
3
PP4 PCl6 2 PCl6 2
(D) <1

32. The equilibrium constant for the reaction


26. The reaction between NO(g) and O2(g) to give NO2(g) is N2O4(g) 2NO2(g)
second order in NO (g) and first order in O2(g). By what
factor will the reaction rate change if the concentrations is 6.10 103 at 25C. Calculate the value of K for this
of both reactants are doubled? reaction:
NO2(g) 1 /2N2O4(g)
(A) 2 (B) 4 (C) 6 (D) 8
(A) 327 (B) 164
27. The decomposition of ethane into two methyl radicals (C) 12.8 (D) 3.05 103
has a first order rate constant of 5.5 104 sec1 at
700 C. What is the half-life for this decomposition in
minutes? 33. The ion-product constant for water at 45 C is 4.0 1014.
What is the pH of pure water at this temperature?
(A) 9.1 (B) 15 (C) 21 (D) 30
(A) 6.7 (B) 7.0 (C) 7.3 (D) 13.4

28. The dependence of the rate constant of a reaction on


temperature is given by the equation k = e E kT .
a 34. The position of equilibrium lies to the right in each of
Under what conditions is k the smallest? these reactions.
(A) high T and large Ea (B) high T and small Ea N2H5+ + NH3 NH4+ + N2H4

(C) low T and large Ea (D) low T and small Ea NH3 + HBr NH4+ + Br
N2H4 + HBr N2H5+ + Br
29. The reaction Based on this information, what is the order of acid
CHCl3(g) + Cl2(g) CCl 4(g) + HCl(g) strength?
is believed to proceed by this mechanism: (A) HBr > N2H5+ > NH4+ (B) N2H5+ > N2H4 > NH4+
Cl2(g) 2Cl(g) fast (C) NH3 > N2H4 > Br (D) N2H5+ > HBr > NH4+
Cl(g) + CHCl3(g) HCl(g) + CCl3(g) slow
CCl3(g) + Cl(g) CCl 4(g) fast
35. HCN is a weak acid (K a = 6.2 1010). NH3 is a weak
What rate equation is consistent with this mechanism? base (K b = 1.8 105). A 1.0 M solution of NH4CN
(A) Rate = k[Cl2] would be
(B) Rate = k[Cl][CHCl3] (A) strongly acidic (B) weakly acidic
(C) Rate = k[Cl2][CHCl3] (C) neutral (D) weakly basic
(D) Rate = k[Cl2]1/2[CHCl 3]
36. What is the percent ionization of a 0.010 M HCN
solution? (Ka = 6.2 1010)
30. The activation energy of a certain reaction is 87 kJmol1.
What is the ratio of the rate constants for this reaction (A) 0.0025% (B) 0.025%
when the temperature is decreased from 37 C to 15 C? (C) 0.25% (D) 2.5%
(A) 5/1 (B) 8.3/1 (C) 13/1 (D) 24/1

Not valid for use as an USNCO National Examination after April 25, 1999 Page 5
37. How many moles of HCOONa must be added to 1.0 L of Questions 43. and 44. should be answered with reference to the
0.10 M HCOOH to prepare a buffer solution with a pH of reaction.
3.4? (HCOOH K a = 2 104)
2Cr(s) + 3Cu2+(aq) 2Cr3+(aq) + 3Cu(s) E = 0.43 V
(A) 0.01 (B) 0.05 (C) 0.1 (D) 0.2
43. Which expression gives the value for G in kJmol1 for
this reaction at 25 C?
38. The acidbase indicator methyl red has a Ka of 1 105.
Its acidic form is red while its alkaline form is yellow. If (A) 6 8.31 0.43 1000
methyl red is added to a colorless solution with a pH = 7, 6 96500 0.43 1000
the color will be (B)
8.31
(A) pink (B) red (C) orange (D) yellow
6 96500 0.43
(C)
1000
39. Silver ions are added to a solution with 6 8.31 0.43
[Br] = [Cl] = [CO32] = [AsO43] = 0.1 M. (D)
1000
Which compound will precipitate at the lowest [Ag+]?
(A) AgBr (Ksp = 5.0 1013)
44. What is the voltage for this cell when [Cu2+] = 1.0 M and
(B) AgCl (Ksp = 1.8 1010) [Cr3+] = 0.010 M?
(C) Ag2CO3 (Ksp = 8.1 1012) (A) 1.2 (B) 0.87 (C) 0.47 (D) 0.39
(D) Ag3AsO4 (Ksp = 1.0 10 )
22

45. All of these sets of quantum numbers are permissible


40. Consider a voltaic cell based on these halfcells. except
n l ml ms
Ag+(aq) + e Ag(s) E = +0.80 V
Cd (aq) + 2e Cd (s)
2+
E = 0.40 V (A) 1 0 0 + 1 /2
Identify the anode and give the voltage of this cell under (B) 2 2 0 1 /2
standard conditions.
(C) 3 1 1 1 /2
(A) Ag; Ecell = 0.40 V (B) Ag; Ecell = 2.00 V
(D) 3 2 1 + 1 /2
(C) Cd; Ecell = 1.20 V (D) Cd; Ecell = 2.00 V
46. Which element can exhibit more than one oxidation state
in compounds?
41. Which two species react spontaneously? 1. Cr 2. Pb 3. Sr
(A) Cu (s) + Ag+(aq) (B) Br2(l) + Cl(aq) (A) 1 only (B) 1 and 2 only
(C) H2O(l) + Ca2+(aq) (D) Au(s) + Mg2+(aq) (C) 2 and 3 only (D) 1, 2 and 3

42. When aluminum oxide is electrolyzed in the industrial 47. When the isoelectronic species, K+, Ca2+, and Cl, are
process for the production of aluminum metal, aluminum arranged in order of increasing radius, what is the correct
is produced at one electrode and oxygen gas is produced order?
at the other. For a given quantity of electricity, what is
the ratio of moles of aluminum to moles of oxygen gas? (A) K+, Ca2+, Cl (B) K+, Cl, Ca2+
(A) 1:1 (B) 2:1 (C) 2:3 (D) 4:3 (C) Cl, Ca2+,K+ (D) Ca2+, K+, Cl

48. Which Group 2 element has chemical properties least


like the other members of the group?
(A) Be (B) Ca (C) Sr (D) Ba

Page 6 Not valid for use as an USNCO National Examination after April 26, 1999
49. In the vapor state which atom has the largest ionization 56. How many carboncarbon bonds are in a molecule of
energy? 2-methyl-2-butanol?
(A) Na (B) K (C) Mg (D) Ca (A) 2 (B) 3 (C) 4 (D) 5

50. All of these species have the same number of valence 57. Which molecule can exist as stereoisomers?
electrons as NO3 except
(A) CHF=CHF (B) F 2C=CCl2
(A) CO32 (B) HCO3 (C) NF3 (D) SO3
(C) CH2FCHF2 (D) CF3CH3

51. Which set contains no ionic species?


58. What are the most likely products in the reaction between
(A) NH4Cl, OF2, H2S (B) CO2, Cl2, CCl4 CH3CH2CH2OH and HI?
(C) BF3, AlF3, TlF3 (D) I2, CaO, CH3Cl (A) CH3CH2CH2I and H2O
(B) CH3CH2CH3 and HOI
52. When these species are arranged in order of increasing (C) CH3OH and CH3CH2I
bond energy, what is the correct sequence?
(D) ICH2CH2CH2OH and H2
(A) N2, O2, F2 (B) F 2, O2, N2
(C) O2, F2, N2 (D) O2, N2, F2
59. Addition polymers include
1. polyamide 2. polyethylene 3. polyester
53. The geometry of the atoms in the species PCl 4+ is best (A) 1 only (B) 2 only
described as
(C) 2 and 3 only (D) 1, 2 and 3
(A) tetrahedral (B) seesaw
(C) square (D) trigonal bipyramidal
60. All of these are aromatic compounds except
(A) hexene, C6H12
54. Which are nonpolar molecules?
1. NCl3 2. SO3 3. PCl 5 (B) toluene, C6H5CH3

(A) 1 only (B) 2 only (C) p-dichlorobenzene, C6H4Cl2

(C) 1 and 3 only (D) 2 and 3 only (D) naphthalene, C10H8

55. What are the hybridizations of


CH3CHCH2
carbon 1 and carbon 2 in the 1 2
hydrocarbon?
(A) sp3, sp (B) sp3, sp2
(C) sp2, sp2 (D) sp, sp2

END OF TEST

Not valid for use as an USNCO National Examination after April 25, 1999 Page 7
Page 8 Not valid for use as an USNCO National Examination after April 26, 1999
US National Chemistry Olympiad 1999
National ExaminationPart I
SCORING KEY

Number Answer Number Answer Number Answer


1. D 21. C 41. A
2. D 22. A 42. D
3. B 23. A 43. C
4. D 24. A 44. C
5. D 25. A 45. B
6. A 26. D 46. B
7. C 27. C 47. D
8. B 28. C 48. A
9. B 29. D 49. C
10. D 30. C 50. C
11. D 31. D 51. B
12. C 32. C 52. B
13. B 33. A 53. A
14. A 34. A 54. D
15. C 35. D 55. B
16. C 36. B 56. C
17. D 37. B 57. A
18. B 38. D 58. A
19. A 39. A 59. B
20. B 40. C 60. A

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