2022 U.S.

NATIONAL
CHEMISTRY OLYMPIAD
NATIONAL EXAM PART II
Prepared by the American Chemical Society Chemistry Olympiad Examinations Task Force

OLYMPIAD EXAMINATIONS TASK FORCE

Seth N. Brown, Chair, University of Notre Dame, Notre Dame, IN
James Ayers, Colorado Mesa University, Grand Junction, CO Valerie Ferguson, Moore HS, Moore, OK (retired)
Jerry Bell, Simmons University, Boston, MA (retired) Kimberly Gardner, United States Air Force Academy, CO
Jesse Bernstein, Miami Country Day School, Miami, FL (retired) Paul Groves, South Pasadena HS, South Pasadena, CA (retired)
Mark DeCamp, University of Michigan, Dearborn, MI (retired) John Kotz, State University of New York, Oneonta, NY (retired)
Joshua de Groot, College of Southern Idaho, Twin Falls, ID Sarah Leite, Hopkins School, New Haven CT
James Dohm, ExxonMobil, Houston, TX Michael A. Morgan, Francisco Bravo Medical Magnet HS, Los Angeles, CA
Xu Duan, Holton-Arms School, Bethesda, MD Jane Nagurney, Scranton Preparatory School, Scranton, PA (retired)

DIRECTIONS TO THE EXAMINER

All testing materials including scratch paper should be turned in and kept secure until May 14, 2022, after which tests can be returned
to students and their teachers for further study.

When the student has completed Part II, or after one hour and forty-five minutes have elapsed, the student must turn in the Part II
testing materials, and all scratch paper. Be sure that the student has supplied all of the information requested 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 page two for student reference.

Students should be permitted to use non-programmable calculators. The use of a programmable calculator, cell phone, or any
other device that can access the internet or make copies or photographs during the exam is grounds for disqualification.

DIRECTIONS TO THE EXAMINEE - 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.
(Be sure to use the same identification number you used for Part I.). 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 and scratch paper.

Do not forget to turn in your U.S. citizenship/Green Card Holder statement before leaving the testing site today.

Property of ACS USNCO – Not for use as USNCO National Exam after May 1, 2022
Distributed by the American Chemical Society, 1155 16th Street, N.W., Washington, DC 20036
All rights reserved. Printed in U.S.A.
 ABBREVIATIONS AND SYMBOLS CONSTANTS
amount of substance n Faraday constant F molar mass M
ampere A free energy G mole mol R = 8.314 J mol–1 K–1
atmosphere atm frequency ν Planck’s constant h R = 0.08314 L bar mol–1 K–1
atomic mass unit u gas constant R pressure P
F = 96,500 C mol–1
Avogadro constant NA gram g rate constant k
Celsius temperature °C hour h reaction quotient Q F = 96,500 J V–1 mol–1
centi– prefix c joule J second s NA = 6.022 × 1023 mol–1
coulomb C kelvin K speed of light c
h = 6.626 × 10–34 J s
density d kilo– prefix k temperature, K T
electromotive force E liter L time t c = 2.998 × 108 m s–1
energy of activation Ea measure of pressure mm Hg vapor pressure VP 0 °C = 273.15 K
enthalpy H milli– prefix m volt V 1 atm = 1.013 bar = 760 mm Hg
entropy S molal m volume V
equilibrium constant K molar M year y Specific heat capacity of H2O =
4.184 J g–1 K–1

EQUATIONS

RT  −∆H o   1   k2  Ea  1 1 
E Eo −
= ln Q =ln K     + constant ln=
   − 
nF  R  T   k1  R  T1 T2 

1 PERIODIC TABLE OF THE ELEMENTS 18

1A 8A
1 2
H 2 13 14 15 16 17 He
1.008 2A 3A 4A 5A 6A 7A 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 3 4 5 6 7 8 9 10 11 12 Al Si P S Cl Ar
22.99 24.31 3B 4B 5B 6B 7B 8B 8B 8B 1B 2B 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 78.97 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 95.95 (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
132.9 137.3 138.9 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 (209) (210) (222)
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
(223) (226) (227) (261) (262) (263) (262) (265) (266) (281) (272) (285) (286) (289) (289) (293) (294) (294)

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) (244) (243) (247) (247) (251) (252) (257) (258) (259) (262)

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Question 1 (page 1 of 1) USNCO ID Number:
1. [11%] Compound A contains only carbon, fluorine, and chlorine.
a. The vapor density of A at 1.00 bar and 25.0 °C is 6.895 g L-1. What is the molar mass of A?

b. Chlorofluorocarbons such as A react with sodium metal to convert all the chlorine present into sodium chloride.
The products from the reaction of sodium with 100.0 mL of gaseous A (at 1.00 bar and 25.0 °C) are dissolved
in water and a few drops of sodium chromate solution are added. This solution is then titrated with 0.3540 M
AgNO3 solution until a bright red precipitate appears, which requires 22.79 mL of the titrant. How many
chlorine atoms are there in a molecule of A?

c. What is the molecular formula of A? Justify your answer.

d. There is only one known isomer of A, compound B. The two compounds have nearly identical boiling points,
but can be distinguished by 19F NMR spectroscopy, a technique that is sensitive to small differences in the
chemical environments of fluorine atoms in compounds. When analyzed by this method, compound A exhibits
only a single type of chemical environment for fluorine, while compound B shows two distinct environments
for its fluorine atoms. Draw structural formulas for compounds A and B that are consistent with these
observations.

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Question 2 (page 1 of 2) USNCO ID Number:

2. [13%] A chemist prepares an ammonia/ammonium chloride buffer from solid ammonium chloride, 0.80 M NH3, and
distilled water.
a. What is the pH of the 0.80 M NH3 solution? (The Ka of NH4+ is 5.6 × 10-10.)

b. What mole ratio of ammonia to ammonium chloride is required for the buffer to have pH = 9.20?

c. Calculate the volume of ammonia solution and mass of ammonium chloride needed to make up 500 mL of the
pH = 9.20 buffer with a total concentration of nitrogen-containing species (NH3 or NH4+) of 0.50 mol L-1.

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Question 2 (page 2 of 2) USNCO ID Number:

d. To the solution described in (c) is added 10.0 mL of 0.10 M AgNO3.

i. Some AgCl precipitates from this mixture. Justify that this is the case. The Ksp of AgCl is 1.8 × 10-10
and the Kf of Ag(NH3)2+ is 1.6 × 107.

ii. What is the final concentration of free Ag+ in solution after this mixture achieves equilibrium?

iii. What is the mass of AgCl that precipitates from solution?

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Question 3 (page 1 of 2) USNCO ID Number:

3. [14%] Gaseous molecular and atomic bromine have the following thermodynamic properties:

Species ΔH°f (kJ mol-1) S° (J mol-1 K-1)

Br2(g) 30.9 245.4

Br(g) 111.9 175.0

a. What is the bond dissociation enthalpy (BDE) of the bromine-bromine bond in Br2(g)?

b. How many atoms of Br(g) will be present at equilibrium in a 1.00-L container with 0.100 bar of Br2(g) at 298
K?

c. The ionization energy of Br(g) is 1145.9 kJ mol-1, while the ionization energy of Br2(g) is 1025.1 kJ mol-1.
What is the bond dissociation enthalpy of Br2+(g) (defined as the enthalpy of reaction of Br2+(g) to form Br+(g)
and Br(g))?

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Question 3 (page 2 of 2) USNCO ID Number:

d. Propose an explanation for the difference in BDE between Br2(g) and Br2+(g) in terms of the bonding in these
two species.

e. The vapor pressure of liquid bromine at 298 K is 0.283 bar. What is the absolute entropy S° of Br2(l)?

f. The absolute entropies of the gas-phase atoms of the fourth period given in the table exhibit a non-monotonic
pattern. Explain why the absolute entropies of Se(g) and Br(g) are larger than the absolute entropies of either
As(g) or Kr(g).

As(g) Se(g) Br(g) Kr(g)

S°, J mol-1 K-1 163.2 176.7 175.0 164.1

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Question 4 (page 1 of 3) USNCO ID Number:

4. [14%] Iodide ion reacts with hydrogen peroxide in acidic solution according to the following equation:

2 I–(aq) + H2O2(aq) + 2 H+(aq) → I2(aq) + 2 H2O(l) (4)

The reaction is carried out at 18.8 °C in the presence of a mixture of CH3COOH and NaOH to regulate the pH, sodium
thiosulfate (which reacts very rapidly with I2 to form tetrathionate ions), and starch. All the components except the
hydrogen peroxide are premixed, and then the hydrogen peroxide solution is added and a stopwatch is started. The
solution remains colorless until it suddenly turns blue, at which point the time t is recorded. The following data are
obtained:

Run 1.0 M 1.0 M NaOH, 0.20 M 0.20 M 0.020 M Distilled t, s

CH3COOH, mL KI, mL H2O2, mL Na2S2O3, H2O, mL
mL mL

A 2.0 1.0 2.0 2.0 1.0 2.0 68.2

B 4.0 1.0 2.0 2.0 1.0 0.0 68.9

C 2.0 1.0 4.0 2.0 1.0 0.0 33.2

D 2.0 1.0 2.0 4.0 1.0 0.0 32.9

a. Give a qualitative explanation for why the solution suddenly turns blue after a certain amount of time has
elapsed.

b. Calculate the initial [H+] in runs A and B and explain why [H+] will not change significantly over the course of
the respective reactions. (The Ka of CH3COOH is 1.8 × 10-5.)

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Question 4 (page 2 of 3) USNCO ID Number:

c. The rate law for reaction (4) has the form Rate = k4[I–]m[H2O2]n[H+]p, where m, n, and p are integers. What are
the values of m, n, and p under these experimental conditions? Briefly explain your reasoning.

d. What is the value of the rate constant k4 for this reaction?

e. The following mechanism for reaction (4) has been proposed:

H2O2(aq) + H+(aq) ⇄ H3O2+(aq) (fast, unfavorable)

H3O2+(aq) + I–(aq) → HOI(aq) + H2O(l) (slow)

HOI(aq) + H+(aq) ⇄ H2OI+(aq) (fast, unfavorable)

H2OI+(aq) + I–(aq) → I2(aq) + H2O(l) (fast)

Is this mechanism consistent with the given data? Justify your answer.

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Question 4 (page 3 of 3) USNCO ID Number:

f. The experiments are repeated under the same conditions as Runs A and B above, except that phosphoric acid
(H3PO4, Ka = 7.6 × 10-3) is substituted for acetic acid. The observed times for the solutions to turn blue with
this substitution are 46.7 s and 31.5 s, respectively. Propose an interpretation for these observations.

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Question 5 (page 1 of 1) USNCO ID Number:

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. Diiodine pentoxide is added to a barium hydroxide solution.

b. Sulfur dioxide is bubbled through an acidified solution of potassium permanganate.

c. Iron(III) oxide is heated with carbon monoxide gas at 1200 °C.

d. Aqueous hydrobromic acid is electrolyzed at platinum electrodes.

e. 1-Butanol reacts with an acidified solution of potassium dichromate.

f. Oganesson-294 undergoes alpha decay.

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Question 6 (page 1 of 2) USNCO ID Number:

6. [12%] A galvanic cell is constructed at 298 K with one half-cell consisting of a 10.00 g silver wire immersed in 1.00 L of
a 0.100 M solution of silver nitrate and the second half-cell consisting of a 20.00 g copper plate immersed in 1.00 L of a
0.200 M solution of copper(II) sulfate.

Half-reaction E°, V

Ag+(aq) + e– → Ag(s) 0.800

Cu2+(aq) + 2e– → Cu(s) 0.337

a. What voltage is measured for this galvanic cell?

b. The cell is discharged at a constant current of 0.150 A until the mass of the silver electrode is equal to the mass
of the copper electrode. How much time does this take?

c. A chemist wishes to add sodium oxalate to one of the half-cells in the original cell to decrease the measured
voltage. To which cell should the sodium oxalate be added, and why?

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Question 6 (page 2 of 2) USNCO ID Number:

d. What mass of sodium oxalate would need to be added to the appropriate half-cell to cause the voltage in the
original cell to become 0.200 V? You may assume that there is no change in the volume of the solution. The
Ksp of Ag2C2O4 is 3.5 × 10-11 and the Ksp of CuC2O4 is 3.0 × 10-8.

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Question 7 (page 1 of 1) USNCO ID Number:

7. [12%] Formamide and glyoxal are six-atom molecules with essentially planar structures as depicted below (these are
NOT Lewis structures).

a. Draw complete Lewis structures for these two molecules, including all bonds, lone pairs, and nonzero formal
charges.

b. One of these compounds has a normal boiling point of 51 °C, while the other has a normal boiling point of 210
°C. Assign which compound has which boiling point, and propose an explanation for the large difference.

c. The H–N–H bond angle in formamide (122°) is much larger than the H–N–H angle in ammonia (107°).
Explain this difference.

d. Rotation of the central bond in the two molecules (the C-N bond in formamide or the C-C bond in glyoxal)
occurs at very different rates, with the barrier to rotation in formamide being much larger (74 kJ mol-1 vs. 25 kJ
mol-1). Explain why rotation is much more difficult in formamide than in glyoxal.

Page 14 Property of ACS USNCO – Not for use as USNCO National Exam after May 1, 2022
Question 8 (page 1 of 2) USNCO ID Number:

8. [12%] Consider the following isomers with the formula C3H6O2.

a. Rank the three compounds in order of increasing normal boiling point, and justify your ordering.

b. Compounds A–C are all optically inactive. Draw the structure of an optically active isomer of C3H6O2.

c. Compounds A and B react reversibly with water in the presence of a suitable catalyst as shown below:

Which reaction has the larger equilibrium constant? Explain your answer in terms of the structure or bonding of
the species in the reactions.

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Question 8 (page 2 of 2) USNCO ID Number:

d. Compound C reacts with water in the presence of a strong acid to form two new organic compounds. Write a
balanced equation for this reaction, including structural formulas for the two organic products.

e. In the presence of excess strong base, compound C reacts with water irreversibly. Explain why this reaction is
irreversible while the reaction in the presence of acid is reversible.

Page 16 Property of ACS USNCO – Not for use as USNCO National Exam after May 1, 2022
 2022 USNCO Part 2 Solutions

1. a. PV = nRT, so n = PV/RT. 1.000 L of gas will have

n = (1.000 bar)(1.000 L)/(298.15 K)(0.08314 L bar mol-1 K-1)
n = 0.04034 mol
molar mass = (6.895 g L-1)/(0.04034 mol L-1) = 170.9 g mol-1

b. 0.02279 L titrant × 0.3540 mol L-1 = 8.068 × 10-3 mol chloride

100.0 mL gas has n = (1.000 bar)(0.1000 L)/(298.15 K)(0.08314 L bar mol-1 K-1)
= 4.034 × 10-3 mol A
(8.068 × 10 mol chloride)/(4.034 × 10-3 mol A) = 2.000 mol Cl/mol A
-3

c. Since the molar mass of A is 170.9 and there are 2 mol Cl per mol A, the carbons and
fluorines in A must have a combined mass of 170.9 – 2(35.45) = 100.0 amu. If A has
only one carbon, it must have (100.0 – 12.01)/19.00 = 4.63 F atoms, which is impossible
(it must have an integer number of each type of atom per formula unit, plus over six
halogens per carbon atom is not chemically reasonable). Two carbons in A would imply
(100.0 – 2×12.01)/19.00 = 4.00 atoms of F, which is possible. Each additional carbon in
the formula would result in 0.63 fewer F atoms, which will not be especially close to an
integer from 3-7 carbon atoms, at which point there would need to be fewer than one F
atom. Thus the only possibility is C2F4Cl2.

d.

1
 2022 USNCO Part 2 Solutions

2. a. The major reaction is:

NH3(aq) + H2O(l) NH4+(aq) + OH–(aq) Keq = (Kw/Ka of NH4+)
Keq = (1 × 10-14)/(5.6 × 10-10)
Keq = 1.8 × 10-5
Since this is the major reaction, [NH4+] ≈ [OH–], and since it is not very favorable,
[NH3] ≈ 0.80 M.
[NH4+ ][OH − ] [OH − ]2
= = 1.8 × 10-5
[NH3 ] [0.80]
[OH–]2 = 1.44 × 10-5
[OH–] = 3.8 × 10-3 M
pH = 14 + log[OH–] = 11.60

b. pH = pKa of NH4+ + log([NH3]/[NH4+])

9.20 = 9.25 + log([NH3]/[NH4+])
log([NH3]/[NH4+]) = –0.05
[NH3]/[NH4+] = 0.89

c. There are two constraints on the number of moles of NH3 and of NH4+. From the fact
that the total concentration of nitrogen species is 0.500 M in 0.500 L,
(mol NH3) + (mol NH4+) = 0.250 mol
From the calculation in (b),
(mol NH3) = 0.89(mol NH4+)
Solving the two simultaneous equations gives:
0.89(mol NH4+) + (mol NH4+) = 0.250 mol
(mol NH4+) = 0.132 mol
0.132 mol NH4+ × (53.49 g NH4Cl/mol) = 7.06 g NH4Cl

(mol NH3) = 0.89(mol NH4+) = 0.89(0.132 mol) = 0.117 mol NH3

0.117 mol NH3/(0.80 M NH3) = 0.147 L of the 0.80 M NH3 solution

d. i. mol Ag+ = (0.0100 L)×(0.10 mol/L) = 0.0010 mol Ag+. Since the amounts of both
chloride and ammonia are over 100 times this amount, we can neglect the changes of
these latter two species as AgCl(s) and Ag(NH3)2+ form. So [Cl–] = 0.132 mol/(0.510 L)
= 0.259 M and [NH3] = 0.117 mol/(0.510 L) = 0.229 M.
There are a number of ways to approach the analysis of whether a precipitate
forms. Let us assume that no precipitate forms, so all of the Ag+ (initial concentration =
0.0010 mol/0.51 L = 1.96 × 10-3 M) remains in solution. Of course, much of it will be in
the form of the complex ion:
[Ag(NH3 )+2] [Ag(NH3 )+ 2]
+ 2 = = Kf = 1.6 × 107
[Ag ][NH3 ] [Ag ][0.229]2
+
[Ag(NH3 )+ 2]
+ = 8.4 × 105
[Ag ]
This means that almost all the silver ion in solution is in the form of the complex
ion, so [Ag+] = [Ag(NH3)2+]/(8.4 × 105) = (1.96 × 10-3)/(8.4 × 105) = 2.3 × 10-9 M.

2
 2022 USNCO Part 2 Solutions

Qsp = [Ag+][Cl–] = [2.3 × 10-9][0.259] = 6.0 × 10-10 > Ksp. This means that there will be a
precipitate of AgCl.

ii. Since there is a precipitate, [Ag+][Cl–] = Ksp

[Ag+][0.259] = 1.8 × 10-10
[Ag+] = 6.95 × 10-10 M

iii. From the complexation equilibrium,

[Ag(NH3 )+ 2] [Ag(NH3 )+2]
+ 2 = −10 = Kf = 1.6 × 107
[Ag ][NH3 ] [6.95×10 ][0.229]2
[Ag(NH3)2+] = 5.8 × 10-4 M
This accounts for (5.8 × 10-4 mol/L)×(0.510 L) = 3.0 × 10-4 mol of silver. The amount of
free Ag+ is negligible, so the amount of silver that must have precipitated as AgCl is
(1.00 × 10-3 mol total Ag) – (3.0 × 10-4 mol complexed Ag) = 7.0 × 10-4 mol AgCl.
(7.0 × 10-4 mol AgCl)×(143.4 g mol-1) = 0.100 g AgCl

3
 2022 USNCO Part 2 Solutions

3. a. Br2(g) → 2 Br(g) ∆H°rxn = BDE of Br–Br bond

∆H°rxn = 2(111.9 kJ mol-1) – 30.9 kJ mol-1 = 192.9 kJ mol-1

b. For Br2(g) → 2 Br(g), ∆S° = 2(175.0 J mol-1 K-1) – 245.4 J mol-1 K-1 = 104.6 J mol-1 K-1
∆G° = ∆H° – T∆S° = (192.9 kJ mol-1) – (298 K)(0.1046 kJ mol-1 K-1) = 161.7 kJ mol-1
∆G° = –RTln(Keq)
161700 J mol-1 = –(8.314 J mol-1 K-1)(298 K)ln(Keq)
Keq = 4.5 × 10-29
At equilibrium:
𝑝𝑝Br 2 𝑝𝑝Br 2
= = 4.5 × 10-29
𝑝𝑝Br2 0.100
pBr = 2.1 × 10-15 bar
In a 1.00 L container, PV = nRT:
(2.1 × 10-15 bar)(1.00 L) = n(0.08314 L bar mol-1 K-1)(298 K)
n = 8.6 × 10-17 mol
(8.6 × 10-17 mol)×(6.022 × 1023 mol-1) = 5.2 × 107 Br atoms

c. Using Hess’s Law (all species are gas-phase):

Br2 → 2 Br ∆H° = 192.9 kJ mol-1
Br → Br+ + e– ∆H° = 1145.9 kJ mol-1
Br2+ + e– → Br2 ∆H° = –1025.1 kJ mol-1
Br2+ → Br + Br+ ∆H° = BDE = 313.7 kJ mol-1

d. The electron that is removed from Br2 is π* in character, so the bond order of Br2+ is 1.5
compared to 1.0 for Br2. The higher bond order results in a greater bond strength.

e. ∆G°vap, 298K = –RTln(Keq) = –(8.314 J mol-1 K-1)(298 K)ln(0.283) = 3.13 kJ mol-1

∆G°vap, 298K = ∆H°vap – T∆S°vap
3.13 kJ mol-1 = 30.9 kJ mol-1 – (298 K)(∆S°vap)
∆S°vap = 93.2 J mol-1 K-1
∆S°vap = (S° of Br2(g)) – (S° of Br2(l))
93.2 J mol-1 K-1 = 245.4 J mol-1 K-1 – (S° of Br2(l))
S° of Br2(l) = 152.2 J mol-1 K-1

f. As and Kr have only one way of arranging their valence electrons (for As, each valence p
orbital is half-filled, while Kr has each valence p orbital completely filled). In contrast,
Se and Br have orbitally degenerate ground states, which gives them more ways of
arranging their electrons. This increase in the number of possible arrangements
corresponds to a higher entropy (S = kBlnΩ).

4
 2022 USNCO Part 2 Solutions

4. a. I2 is produced in the reaction between H2O2 and I–. Initially, the I2 does not accumulate
to a significant extent because it immediately reacts with the thiosulfate ion. Once the
small amount of thiosulfate is consumed, then I2 begins to accumulate, and the solution
turns blue because of the intensely blue complex formed between starch and iodine.

b. The NaOH will immediately react with the CH3COOH to form CH3COO–. Taking into
account the 10-fold dilution, this means that in run A, [CH3COOH] = [CH3COO–] = 0.1
M. Since
[H + ][CH3 COO- ]
Ka = 1.8 × 10-5 = [CH3 COOH]
[H+] = 1.8 × 10-5 M
In run B, with [CH3COOH] = 0.3 M and [CH3COO–] = 0.1 M, [H+] = 5.4 × 10-5 M.

These solutions are buffers, with the H+ consumed in reaction 4 being replenished by the
CH3COOH. Thus, at the point where the initially 0.0020 M S2O32- is consumed, the
concentration of CH3COOH will fall to 0.098 M while [CH3COO–] rises to 0.102 M, and
[H+] = 1.73 × 10-5 M, a change of only 4%.

c. In each case, [S2O32-]0 = 0.0020 M, so at the point where the blue color appears, ∆[H2O2]
= –0.0010 M (since two moles of thiosulfate react per mole of I2 produced). Since rate =
–∆[H2O2]/∆t, the time recorded is inversely proportional to the initial rate of the reaction.
Comparing run B to run A, [H+] increases by a factor of 3 while all other
concentrations are the same. The rate is essentially unchanged, so p = 0.
Comparing run C to run A, [I–] increases by a factor of 2 while all other
concentrations are the same. The rate roughly doubles, so m = 1.
Comparing run D to run A, [H2O2] increases by a factor of 2 while all other
concentrations are the same. The rate roughly doubles, so n = 1.
Rate = k4[I–][H2O2]
d. k4 = (–∆[H2O2]/∆t)/([I–][H2O2]). So:
Run A, k4 = (0.0010 M/68.2 s)/([0.040 M][0.040 M]) = 9.1 × 10-3 M-1 s-1
Run B, k4 = (0.0010 M/68.9 s)/([0.040 M][0.040 M]) = 9.2 × 10-3 M-1 s-1
Run C, k4 = (0.0010 M/33.2 s)/([0.080 M][0.040 M]) = 9.4 × 10-3 M-1 s-1
Run D, k4 = (0.0010 M/32.9 s)/([0.040 M][0.080 M]) = 9.5 × 10-3 M-1 s-1
Average = 9.3 × 10-3 M-1 s-1
e. This mechanism predicts Rate = k2[I–][H3O2+] = k2K1[I–][H2O2][H+]. This is inconsistent
with the observed data under these conditions, since it predicts first-order dependence on
[H+] while a zero-order dependence is actually observed.

f. H3PO4 is a much stronger acid than CH3COOH, with [H+] = 7.6 × 10-3 M and 2.3 × 10-2
M in the two new reactions. Even though there was no effect on the rate of reaction in
the reactions run with acetic acid, now increasing [H+] increases the rate! This indicates
that there is an acid-catalyzed pathway for the reaction (perhaps by the mechanism
proposed in (e)) that has become significant at the lower pH of the reactions run in the
presence of phosphoric acid.

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 2022 USNCO Part 2 Solutions

5. a. Ba2+(aq) + OH–(aq) + I2O5(s) → Ba(IO3)2(s) + H2O(l)

b. MnO4–(aq) + SO2(g) + H2O(l) → Mn2+(aq) + SO42–(aq) + H+(aq)
or MnO4–(aq) + SO2(g) + H2O(l) + H+(aq) → Mn2+(aq) + HSO4–(aq)
c. Fe2O3(s) + CO(g) → Fe(s) + CO2(g)
d. H+(aq) + Br–(aq) → H2(g) + Br2(l)

e. + Cr2O72-(aq) + H+(aq) → + Cr3+(aq) + H2O(l)

294 290
f. Og → Lv + 4He

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 2022 USNCO Part 2 Solutions

6. a. The net cell reaction is

2 Ag+(aq) + Cu(s) → 2 Ag(s) + Cu2+(aq)
with E° = 0.800 V – 0.337 V = 0.463 V. The cell is not under standard conditions, so
applying the Nernst equation gives:
E = E° – (RT/nF)ln([Cu2+]/[Ag+]2)
E = (0.463 V) – ((8.314 J mol-1 K-1)(298 K)/2(96500 J V-1 mol-1)ln([0.200]/[0.100]2)
E = 0.425 V

b. Ag deposition will take place with (107.9 g mol-1)/(96500 C mol-1) = 1.118 × 10-3 g C-1.
Cu dissolution will require (63.55 g mol-1)/2(96500 C mol-1) = 3.293 × 10-4 g C-1.
So if x = the amount of charge passed in the discharge, then
10.00 g + (1.118 × 10-3 g C-1)x = 20.00 g – (3.293 × 10-4 g C-1)x
10.00 g = (1.447 × 10-3 g C-1)x
x = 6909 C
Since q = it,
6909 C = (0.150 A)t
t = 46100 s = 12.8 h

c. Decreasing the voltage means making the net reaction less favorable, which would
involve either decreasing the concentration of the reactants or increasing the
concentration of the products. Adding oxalate would cause precipitation of the insoluble
oxalate salt, so one would need to do that to the silver-containing half-cell to decrease the
voltage.

d. Using the Nernst equation,

0.200 V = (0.463 V) – ((8.314 J mol-1 K-1)(298 K)/2(96500 J V-1 mol-1)ln([0.200]/[Ag+]2)
–0.263 V = 0.021 V + 0.02567ln[Ag+]
[Ag+] = 1.567 × 10-5 M
From the Ksp expression, [Ag+]2[C2O42-] = [1.567 × 10-5]2[C2O42-] = 3.5 × 10-11
[C2O42-] = 0.143 M
This requires the addition of 0.143 mol Na2C2O4 (to achieve this concentration in 1.00 L
of solution) + 0.0500 mol Na2C2O4 (to precipitate 0.0500 mol Ag2C2O4) = 0.193 mol
Na2C2O4. The molar mass of Na2C2O4 is 134.00 g mol-1, so this is 0.193 mol × 134.00 g
mol-1 = 25.9 g Na2C2O4.

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 2022 USNCO Part 2 Solutions

7. a. (Either resonance structure of formamide would be acceptable.)

b. Formamide has the higher normal boiling point because it is capable of forming strong
intermolecular N–H•••O hydrogen bonds.

c. In order to form a partial C–N π bond, as indicated by the minor resonance structure
shown above, the nitrogen must have an unhybridized p orbital and thus must be sp2-
hybridized. The bond angles will be close to 120°. In NH3, the nitrogen is sp3-
hybridized and has bond angles close to 109.5°.

d. The partial π bond in formamide requires the unhybridized p orbital on nitrogen to be

parallel to the p orbital on carbon. Rotating about the carbon-nitrogen bond causes the
two p orbitals to lose overlap and thus diminishes the bonding, leading to a large
energetic cost. No such cost is incurred in glyoxal, where the carbon-carbon bond is
purely σ in character.

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 2022 USNCO Part 2 Solutions

8. a. C (bp 57 °C) < A (bp 92 °C) < B (bp 141 °C)

Only B is capable of forming hydrogen bonds, so it has by far the highest boiling
point. C has a more compact structure than A, which leads to weaker London dispersion
forces and a lower boiling point. (The ester is also less polarizable than the ketone +
ether.)

b. Examples include

c. The equilibrium constant is much larger for compound A. Aldehydes are more
electrophilic than carboxylic acids, because the carboxylic acid is stabilized by donation
from the OH oxygen into the C=O π* orbital, as illustrated by the resonance structures
shown below. This resonance stabilization is lost when the carbonyl carbon goes from
sp2 to sp3 hybridization:

d.

e. Keq for the reaction in (d) is close to 1. A strong base will react with the carboxylic acid
to form the carboxylate anion. This reaction is so favorable (Keq > 109) that it renders the
overall reaction essentially irreversible.