2024 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
Monica Marie Arroyo, Pontifical Catholic University of Puerto Rico, Ponce, PR Paul Groves, South Pasadena HS, South Pasadena, CA (retired)
James Ayers, Colorado Mesa University, Grand Junction, CO Nicolas Hamel, Clackamas Community College, Oregon City, OR (retired)
Jerry Bell, Simmons University, Boston, MA (retired) John Kotz, State University of New York, Oneonta, NY (retired)
Jesse Bernstein, Miami Country Day School, Miami, FL (retired) Mariusz Kozik, Canisius College, Buffalo, NY
Alan D. Crosby, Newton South HS, Newton, MA (retired) Sarah Leite, Hopkins School, New Haven, CT
Mark DeCamp, University of Michigan, Dearborn, MI (retired) Michael A. Morgan, Francisco Bravo Medical Magnet HS, Los Angeles, CA
James Dohm, University of Pennsylvania, Philadelphia, PA Jane Nagurney, Scranton Preparatory School, Scranton, PA (retired)
Kimberly Gardner, United States Air Force Academy, CO Anne O'Connor, Cleveland State University, Cleveland, OH

DIRECTIONS TO THE EXAMINER

Part II of this test requires that student answers be written in this test booklet in the spaces provided underneath the questions. Part II
test booklet and scratch paper should be made available to the student only during the examination period. All testing materials including
scratch paper should be collected from students after the examination. Only test booklets should be shipped to the USNCO office
immediately after the national exam and no later than April 22, 2024.
When the student has completed Part II, or after one hour and forty-five minutes have elapsed, the student must turn in Part II of the
testing materials and all scratch paper. Be sure that the student has supplied 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 only 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 use the same identification number you used for Part I and write it on top of each page in
the indicated fields. 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.

STUDENT USNCO ID:

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 ABBREVIATIONS AND SYMBOLS CONSTANTS
amount of substance n Faraday constant F molar mass M 1 1
ampere A free energy G mole mol R = 8.314 J mol– K–
1 1
atmosphere atm frequency ν Planck’s constant h R = 0.08314 L bar mol– K–
atomic mass unit u gas constant R pressure P F = 96,500 C mol–
1

Avogadro constant NA gram g rate constant k 1

F = 96,500 J V–1 mol–
Celsius temperature °C hour h reaction quotient Q 1
centi– prefix c joule J second s NA = 6.022 x 1023 mol–
coulomb C kelvin K speed of light c h = 6.626 x 10–34 J s
density d kilo– prefix k temperature, K T 1
c = 2.998 x 108 m s–
electromotive force E liter L time t
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 Specific heat capacity of H2O =
equilibrium constant K molar M year y 1 1
4.184 J g– K–

EQUATIONS

RT æ -DH o ö æ 1 ö æk ö E æ 1 1 ö
E = Eo - ln Q ln K = ç ÷ ç ÷ + constant ln ç 2 ÷ = a ç - ÷
nF è R øè T ø è k1 ø R è T1 T2 ø

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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Distributed by the American Chemical Society, 1155 16th Street, N.W., Washington, DC
20036 All rights reserved. Printed in U.S.A.
Question 1 (page 1 of 2) USNCO ID Number:
1. [10%] An unknown salt MX2 is a group 2 metal halide.
a. 10.00 g MX2 dissolves in 50.0 g water to give a homogeneous solution. The freezing point of this solution is –4.50
°C. What is the molar mass of MX2? For water, Kf = 1.86 °C/m.

b. 10.00 g Na2CO3 and 10.00 g MX2 are mixed in 200.0 mL of water. A precipitate of MCO3 forms. What is the pH
of the supernatant? The Ka of H2CO3 is 4.3 ´ 10-7 and the Ka of HCO3– is 4.7 ´ 10-11

c. A solution of 10.00 g MX2 in water is treated with excess silver nitrate. The precipitate is dried; the mass of the
dried compound is 15.2 g. What is the identity of MX2?

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Question 1 (page 2 of 2) USNCO ID Number:
d. A sample of 10.00 g MX2 dissolved in 50 mL water is treated with increasing amounts of Na2SO4 up to 10 g in total.
How will the mass of precipitate formed vary with the mass of added Na2SO4? Graph your answer on the grid
provided.

e. What color flame test does MX2 give?

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Question 2 (page 1 of 2) USNCO ID Number:
2. [13%] A sample of solid calcium fluoride is suspended in water in an unreactive container and stirred until it achieves
equilibrium. The pH of the solution is lowered by careful addition of nitric acid, and the pH and concentration of
Ca2+(aq) are noted at several points as shown on the graph below. Note that the units on the y axis are millimoles
per liter.

a. Determine the Ksp of CaF2 from the data provided.

b. Qualitatively, what is the cause for the increase in solubility of CaF2 at low pH?

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Question 2 (page 2 of 2) USNCO ID Number:
c. From the data provided, determine the Ka of HF.

d. How many moles of HNO3 must be added to the CaF2/water mixture to achieve a pH = 3.00 in this experiment? The
volume of solution is 1.00 L.

e. Carbon dioxide dissolves in water at 25 °C and 1 atm pressure to the extent of 0.0345 mol L-1. An aliquot of the
solution taken from the above experiment at pH = 5 is stirred under 1 atm CO2 and the pH slowly raised by addition
of solid NaOH until CaCO3 just begins to precipitate. What is the pH of the solution at this point? The Ksp of
CaCO3 is 8.7 ´ 10-9, the Ka of aqueous CO2 (“H2CO3”) is 4.3 ´ 10-7, and the Ka of HCO3– is 4.7 ´ 10-11.

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Question 3 (page 1 of 2) USNCO ID Number:
3. [13%] Ethene, C2H4, can react in the gas phase in the presence of radicals R to form polyethylene as shown in the
equation below. Here n is the degree of polymerization. The forward reaction is second-order while the reverse
reaction is first-order. The values of these rate constants are independent of the degree of polymerization n and the
identity of R.
kf
C2H4(g) + •CH2(CH2)2nCH2R •CH2(CH2)(2n+2)CH2R
kr

a. A sample of polyethylene has an average degree of polymerization n = 1200. How many polymer chains are present
in 1.0 g of this material?

b. Calculate ∆H° and ∆S° for the polymerization reaction.

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Question 3 (page 2 of 2) USNCO ID Number:
c. The bond dissociation enthalpy (BDE) for a typical carbon-carbon single bond is 345 kJ mol-1. From the data given,
what is the BDE of the carbon-carbon double bond in ethene?

d. Ethene is charged to a fixed vessel at 25 bar and 720 K. Traces of radical are then added to initiate polymerization.
What is the percent conversion of ethene into polymer at equilibrium under these conditions?

e. In the presence of a catalyst for the polymerization reaction, the forward rate constant as a function of temperature is
ln(kf) = –3050(1/T) + 21.0. By what factor does the catalyst accelerate the rate of the forward reaction at 500 K?

f. By what factor does the catalyst change the rate of the reverse reaction at 500 K?

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Question 4 (page 1 of 3) USNCO ID Number:
4. [13%] Copper(II) forms a complex ion with ammonia, Cu(NH3)42+, with Kf = 1.7 ´ 1013. An electrochemical cell is set up
as shown below at 298 K. Half-cell A contains 100 mL of 1.00 M Cu(NO3)2, while half-cell B contains 100 mL of
a solution that contains a small amount of copper(II) and is 0.100 M in NH3. A solution of nitric acid is slowly
added to half-cell B and the potential measured by the voltmeter is recorded as a function of the added volume of
HNO3.

buret containing
HNO3 solution

voltmeter

salt bridge

Cu
Cu

1 M Cu2+ 0.100 M NH3

small amt. of Cu(II)

Half-cell A Half-cell B
a. Which half-cell is the cathode and which is the anode? Justify your answer.

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Question 4 (page 2 of 3) USNCO ID Number:
b. Qualitatively explain the shape of the graph.

c. What is the total concentration of copper(II) in the solution in half-cell B?

d. What is the concentration of nitric acid in the buret?

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Question 4 (page 3 of 3) USNCO ID Number:
e. Suppose that the experiment is set up again with silver metal in place of copper metal and silver(I) ion in place of
copper(II) ion, but with all concentrations and all other reagents identical. What would the graph of E vs. mL added
HNO3 look like in this experiment? Sketch your result on the grid below (the graph shown above is redrawn for
your convenience), and explain your answer. Silver(I) forms a complex ion with ammonia, Ag(NH3)2+, with Kf =
1.7 ´ 107.

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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, and clearly show stereochemistry where relevant. You need not balance the equations or show the
phase of the species.

a. Aqueous ammonia and acetic acid are mixed.

b. Sodium iodate is added to an excess of hydriodic acid.

c. Manganese(IV) oxide is added to concentrated aqueous hydrochloric acid.

d. Propyl benzoate is heated with aqueous sodium hydroxide.

e. Calcium oxide and graphite are heated to 2200 °C.

f. Iodine-124 undergoes radioactive decay by electron capture.

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Question 6 (page 1 of 2) USNCO ID Number:
6. [14%] Consider the properties of the group 1 elements, whose valence shell electron configuration is ns1, in the table
below.

Element M n First ionization Energy required to excite the valence Molar density of
energy, kJ mol-1 electron to the (n+1)s orbital, kJ mol-1 solid MCl, mol cm-3
H 1 1312 984 0.0403
Li 2 520 325 0.0507
Na 3 496 308 0.0371
K 4 420 252 0.0266
Rb 5 403 241 0.0232
Cs 6 376 222 0.0237

a. Rationalize the observed trend in first ionization energies with increasing n.

b. Suppose a hydrogen atom were excited to its 2s1 state. If that excited state atom were to transfer its electron to Cs+
to form a ground-state Cs atom, how much energy would that reaction absorb or release?

c. All but one of the atoms listed in the table have an excited state that is significantly lower in energy than the (n+1)s1
state described in the table. Explain this observation, noting which atom is the exception and why.

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Question 6 (page 2 of 2) USNCO ID Number:
d. All but one of the atoms listed in the table have an excited state that is modestly higher in energy (38 – 55 kJ mol-1)
than the (n+1)s1 state described in the table. Explain this observation, noting which atom is the exception and why.

e. The compounds MCl(s) show a smooth decrease in their molar densities, except that HCl(s) is less dense than
expected from the trend and CsCl(s) is more dense than expected. Explain this periodic trend, and give reasons for
the two exceptions to the trend.

137
f. Cs (136.9070895 amu) undergoes radioactive decay to give a stable product whose atomic mass is 136.9058274
amu. What type of radioactive decay is this, and what is the identity of the decay product?

g. Calculate the energy, in kJ mol-1, released by the radioactive decay of 137Cs.

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Question 7 (page 1 of 2) USNCO ID Number:
7. [13%] Flash vacuum pyrolysis of carbonyl azide (CON6) at 420 °C gives low yields of a cyclic compound, diazirinone, as
shown in the equation below. Note that the illustrations of carbonyl azide and diazirinone correctly show the
connectivity of the atoms but are NOT correct Lewis structures. The bond dissociation enthalpies (BDE, in
kJ mol-1) of various bonds among carbon, oxygen, and nitrogen are given in the table.
O
O
C
N N N C N N N + 2 N2
N N
carbonyl azide diazirinone

Bond BDE, kJ mol-1 Bond BDE, kJ mol-1 Bond BDE, kJ mol-1 Bond BDE, kJ mol-1
C–O 350 C–N 290 N–N 160 N–O 200

C=O 741 C=N 615 N=N 418 N=O 480

CºO 1080 CºN 891 NºN 949

a. Draw complete Lewis structures for carbonyl azide and for diazirinone, including all lone pairs and nonzero formal
charges. You need only draw one Lewis structure for each molecule, even if there are multiple possible resonance
structures.

b. Diazirinone decomposes in the gas phase over the course of several days at room temperature to give carbon
monoxide and nitrogen gas. Based on the given BDEs, calculate ∆H° for this decomposition reaction.

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Question 7 (page 2 of 2) USNCO ID Number:
c. The actual ∆H° for the decomposition of diazirinone is –347 kJ mol-1. Comment on any discrepancy you find
between this value and the value you determined in part b. Be sure your comment addresses the direction of
deviation of the two values.

d. Will ∆G° for decomposition at 298 K be algebraically greater than, less than, or equal to ∆H° for decomposition?
Briefly justify your answer.

e. There is an isomer of diazirinone that has a chain structure with the connectivity NCNO. Draw a Lewis structure for
this molecule and clearly describe or sketch its geometry.

f. Would you expect acyclic NCNO to be more or less stable than diazirinone? Clearly justify your prediction.

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Question 8 (page 1 of 2) USNCO ID Number:
8. [12%] Consider the three isomers of C4H9NO2 shown below:
O O H
HO OH
CH3O NH2 H 2N OCH3 N

I II III

a. Which compound is the most basic? Justify your answer.

b. Draw the structures of the conjugate acids of the three compounds.

c. Draw the structure of a chiral isomer of C4H9NO2.

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Question 8 (page 2 of 2) USNCO ID Number:
Consider the two nitrogen heterocycles shown below:
CH3 CH3
N N

N
IV V
d. Which compound is more basic? Draw the structure of its conjugate acid.

e. Which compound is more reactive towards Br2? Explain why it is more reactive and draw the structure of a major
product of its reaction with Br2.

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 2024 USNCO Part 2 Solutions

1. a. (–4.50 °C)/(–1.86 °C/m) = 2.42 m

Since MX2 gives 3 moles of ions per mole of compound, the solution is (2.42 m/3) =
0.807 m.
(0.807 mol MX2/kg water) ´ (0.0500 kg water) = 0.0404 mol MX2
10.00 g MX2/0.0404 mol = 248 g mol-1

b. 10.00 g Na2CO3/(105.99 g mol-1) = 0.09435 mol Na2CO3.

After reaction with 0.0404 mol MX2, approximately 0.0404 mol MCO3 will precipitate,
leaving behind 0.0540 mol CO32- in solution. In 200 mL, this gives a 0.270 M solution of
CO32-. The carbonate ion reacts with water as follows:
CO32-(aq) + H2O(l) ⇌ HCO3–(aq) + OH–(aq) Keq = Kw/(Ka of HCO3–)
[HCO& &
% ][OH ]
= 2.1 ´ 10-4
[CO(&
% ]
[OH & ](
= 2.1 ´ 10-4
[).+,)]
[OH–] = 7.6 ´ 10-3 M
pH = 14 + log10[OH–] = 11.88

c. 15.2 g AgX/(0.0404 • 2 mol X) = 188 g mol-1 of AgX

Since the atomic mass of Ag is 107.9, the molar mass of X is 80 => X is Br.
Subtracting the mass of 2 Br from 248 g mol-1 molar mass of MX2 gives an atomic mass
of M = 88. Thus M = Sr.

d. 0.0404 mol SrSO4 ´ 183.69 g mol-1 = 7.42 g SrSO4 is the maximum amount of
precipitate that can form. The amount actually formed will increase linearly until 0.0404
mol Na2SO4 (= 5.74 g) are added, then will not increase further as Sr2+ becomes the
limiting reagent.

e. Sr gives a red flame test.

1
 2024 USNCO Part 2 Solutions

2. a. From the graph, the molar solubility of CaF2 at high pH is about 0.21 mmol/L, so [Ca2+]
= 2.1×10-4 M and [F–] = 2[Ca2+].
Ksp = [Ca2+][F–]2 = (2.1 × 10-4)(4.2 × 10-4)2 = 3.7 × 10-11

b. F– reacts with H+ to form HF, lowering the concentration of F– and shifting the solubility
equilibrium to cause more solid CaF2 to dissolve.

c. Choosing any low-pH point should work, but it is better to choose a point with pH < 3 so
that the error from reading the plot is minimized. As an example, we can use pH = 2
(1.36 × 10-3 M = [Ca2+]). At this point, [H3O+] = 10–pH = 0.010 M. One can determine
the concentration of F– from the Ksp:
Ksp = [Ca2+][F–]2
3.7 × 10-11 = [1.36 × 10-3][F–]2
[F–] = 1.65 ´ 10-4 M
2+
Since each Ca in solution must be accompanied by two fluorines (in whatever form),
[F–] + [HF] = 2[Ca2+]
[1.65 ´ 10-4] + [HF] = 2[1.36 × 10-3]
[HF] = 2.56 ´ 10-3 M
One can then solve for Ka:
[H% O- ][F – ] [).)0][1.65×0)&5 ]
Ka = = = 6.4 ´ 10-4
[HF] [2.56×0)&% ]

d. At pH = 3, from the graph, [Ca2+] = 3.9 ´ 10-4 M, so [F–] + [HF] = 7.8 ´ 10-4 M. At this
pH, [H3O+] = 1.0 ´ 10-3 M, so
[0.001][F – ]
6.4 ´ 10-4 =
[HF]
–
[F ]/[HF] = 0.64
(7.8 ´ 10-4 – [HF]) = 0.64[HF]
[HF] = 4.8 ´ 10-4 M
The added nitric acid either protonates fluoride ion or produces H3O+. So
mol added HNO3 = mol HF + mol H3O+
mol added HNO3 = 4.8 ´ 10-4 + 1.0 ´ 10-3
Total of 1.5 ´ 10-3 mol added HNO3
2+ -4
e. [Ca ] = 2.1 ´ 10 M. From the Ksp,
[Ca2+][CO32-] = 8.7 ´ 10-9
[CO32-] = 4.1 ´ 10-5 M
One can relate the concentration of CO32- to the concentration of H2CO3 by combining
the two acid-base dissociations:
H2CO3 + 2 H2O ⇌ CO32- + 2 H3O+
Keq = (Ka of H2CO3)(Ka of HCO3–) = 2.0 ´ 10-17
[CO(& - (
% ][H% O ]
= 2.0 ´ 10-17
[H( CO% ]
[8.0 ´ 0)&: ][H% O- ](
= 2.0 ´ 10-17
[).);8<]
[H3O+] = 1.3 ´ 10-7 M
pH = 6.88

2
 2024 USNCO Part 2 Solutions

3. a. M = 1200(28.05 g mol-1) = 3370 g mol-1

Thus 1.0 g polymer = 3.0 ´ 10-5 mol = 1.8 ´ 1019 molecules

b. Keq = kf/kr, so ln(Keq) = ln(kf) – ln(kr) = 10500(1/T) – 16.5

Since ∆G° = –RTln(Keq) = ∆H° – T∆S°, ln(Keq) = –(∆H°/R)(1/T) + (∆S°/R)
∆H° = –10500R = –87.3 kJ mol-1
∆S° = –16.5R = –137 J mol-1 K-1
c. ∆H°rxn = {BDE of C=C} – 2´{BDE of C–C} = –87.3 kJ mol-1
{BDE of C=C} – 2´(345 kJ mol-1) = –87.3 kJ mol-1
{BDE of C=C} = 603 kJ mol-1
d. Since the properties of the shorter and longer polymer radicals are the same, their
concentrations are effectively equal, so Kp = 1/PC2H4.
Kp = kf/kr = 0.147 at 720 K
So at equilibrium PC2H4 = 6.8 bar. Thus 6.8/25 ´ 100% = 27% unreacted ethene, 73%
incorporation into polymer.
e. From the equations:
kf (uncatalyzed, 500 K) = 1310 bar-1 s-1
kf (catalyzed, 500 K) = 2.96 ´ 106 bar-1 s-1
kcat/kuncat = 2300
The catalyzed reaction is 2300 times faster than the uncatalyzed one.
f. Since addition of a catalyst cannot change Keq, the reverse reaction must also be
accelerated by a factor of 2300 by the catalyst.

3
 2024 USNCO Part 2 Solutions

4. a. Half-cell B has a much lower concentration of Cu2+(aq). Not only is it stated that there is
only a small amount of Cu(II), at [NH3] = 0.1 M, almost all copper will be in the form of
Cu(NH3)42+. Since current will flow spontaneously in a concentration cell in a direction
that tends to equalize the concentrations in the two half-cells, reduction of Cu(II) will
happen preferentially in half-cell A, which is thus the cathode. Half-cell B is the anode.

b. As HNO3 is added, it protonates NH3 and decreases its concentration. Less NH3 means a
higher concentration of uncomplexed Cu2+ and hence a smaller voltage. When all the
NH3 is protonated, then all the Cu(II) is in the form of Cu2+(aq), which does not change
further, so the voltage is stable after the endpoint.

c. The easiest way to solve this is to use the potential past the endpoint, where the copper is
in the form of Cu2+(aq). From the graph, E = 0.14 V:
E = E° – (RT/nF)ln([Cu2+]B/[Cu2+]A)
2+
With n = 2, [Cu ]A = 1.00:
0.14 = 0 – (0.0128)ln([Cu2+]B)
[Cu2+] = 1.8 ´ 10-5 M

d. The endpoint is at 3.15 mL, at which point the NH3 has been neutralized:
0.100 L solution ´ 0.100 mol L-1 NH3 = C ´ 0.00315 L HNO3 solution
C = 3.2 M

e. In the original titration, before the endpoint, the Cu(II) is almost all complexed, so:
[Cu(NH% )(-
5 ] [1.8 ×1)&: ]
Kf = 1.7 ´ 1013 = =
[Cu(- ][NH % ]5 [Cu(- ][NH% ]5
[Cu ] = 1.1 ´ 10 [NH3]–4
2+ -18

E = (–0.0128)ln((1.1 ´ 10-18)[NH3]–4)
E = 0.53 + 0.51•ln[NH3]
Repeating the calculation for Ag(I), which differs in the magnitude and expression for Kf
and has n = 1 rather than n = 2:
[Ag(NH% )-
(] [1.8 ×1)&: ]
Kf = 1.7 ´ 107 = =
[Ag - ][NH % ]( [Ag - ][NH% ](
[Ag ] = 1.1 ´ 10 [NH3]–2
+ -12

E = (–0.0257)ln((1.1 ´ 10-12)[NH3]–2)
E = 0.71 + 0.51•ln[NH3]
So before the endpoint, the Ag experiment will give potentials that are 0.18 V higher than
the correspoding values for the Cu experiment.
After the endpoint, the only difference between the Cu and Ag experiments is that n = 1
for Ag (vs. n = 2 for Cu). This results in a doubling of the cell potential for Ag. So:

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2024 USNCO Part 2 Solutions

5
 2024 USNCO Part 2 Solutions

5. a. NH3 + CH3COOH ® NH4+ + CH3COO–

b. IO3– + H+ + I– ® I3– + H2O (I2 also acceptable in place of I3–)
c. MnO2 + H+ + Cl– ® Mn2+ + H2O + Cl2
O O
+ OH– OH +
O O

d.

e. CaO + C ® CaC2 + CO
124
f. I ® 124Te

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 2024 USNCO Part 2 Solutions

6. a. Electron energies are proportional to –Zeff2/n2. For the valence electrons, Zeff only
increases slightly going down a column of the periodic table, so electrons with larger
values of n have higher energies and thus are easier to ionize.

b. The 2s1 state of H has an energy = –1312 kJ mol-1 + 984 kJ mol-1 = –328 kJ mol-1. This
is higher in energy than the valence electron in Cs at –376 kJ mol-1, so the electron
transfer to Cs+ will release 48 kJ mol-1 of energy.

c. In all cases except H, the ns electron can be promoted to an np orbital, which is

significantly lower in energy than the (n+1)s orbital. There is no 1p orbital, so this is not
possible for H.

d. In all cases except H, the (n+1)p orbital is modestly higher in energy than the (n+1)s
orbital, giving rise to an excited state of modestly higher energy. For H, there is a 2p
orbital, but in one-electron atoms the energy depends only on n, not l, so its energy is the
same as that of the 2s state.

e. For Li – Rb, the MCl(s) compounds form ionic lattices with the rock salt structure. As
the cations increase in size going down the column, the lattices expand and hence the
molar density decreases. HCl(s) is a molecular crystal, and the weaker intermolecular
forces give relatively long intermolecular distances and hence a less dense packing.
CsCl(s) adopts a different lattice than the rock salt lattice (it is commonly called the CsCl
lattice), which allows it to pack more densely than the rock salt lattice with a cation the
size of cesium would.

f. b– decay forms 137Ba.

g. E = ∆mc2. ∆m = –1.26 ´ 10-3 amu ´ (1.661 ´ 10-27 kg amu-1) = –2.09 ´ 10-30 kg

E = (2.09 ´ 10-30 kg)(2.998 ´ 108 m s-1)2 = 1.88 ´ 10-13 J = 1.88 ´ 10-16 kJ
(1.88 ´ 10-16 kJ)(6.022 ´ 1023 mol-1) = 1.13 ´ 108 kJ mol-1

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 2024 USNCO Part 2 Solutions

O
O
7. a. C
N N N C N N N
N N
Other resonance structures are acceptable in both cases.

b. ∆H° = S(BDE of bonds broken) – S(BDE of bonds formed)

∆H° = {(N=N) + (C=O) + 2 ´ (C–N)} – {(CºO) + (NºN)}
∆H° = {418 + 741 + 2 ´ 290} – {1080 + 949} kJ mol-1
∆H° = –290 kJ mol-1

c. The reaction is more exothermic than expected, indicating that the bonds are weaker in
the reactant than would be expected based on typical bond dissociation enthalpies. This
is likely due to the three-membered ring in the structure. This means that the bonds in the
ring cannot achieve ideal bond angles, so they are not as strong as expected.

d. ∆S° is highly positive since two molecules are produced from one. Since ∆G° = ∆H° –
T∆S°, ∆G° < ∆H°.

O
N C N
e. , linear at carbon and bent at the middle nitrogen.

f. Entropically, there should be little difference between the molecules. Enthalpically, one
can estimate ∆H° of isomerization from the diazinone to NCNO:
∆H° = {(N=N) + (C=O) + 2 ´ (C–N)} – {(CºN) + (C–N) + (N=O)}
∆H° = {418 + 741 + 2 ´ 290} – {891 + 290 + 480} kJ mol-1
∆H° = 78 kJ mol-1

Even considering that diazirinone is ~57 kJ mol-1 less stable than one would expect (from
the results of b./c.), formation of NCNO is still expected to be endothermic, and thus
diazirinone is expected to be more stable.

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 2024 USNCO Part 2 Solutions

8. a. Compound II is most basic. Nitrogen is the least electronegative atom with a lone pair in
each of the three structures, but in I that lone pair is engaged in resonance with the
carbonyl group; since the resonance is lost on protonation, that nitrogen is not basic. The
oxime III is basic at nitrogen, but the greater amount of s character in the lone pair and
the fact that the nitrogen is bonded to an electronegative oxygen atom, make it less basic
than the amine in II.

b.
H
O O H
HO OH
CH3O NH2 H 3N OCH3 N c.
H
I II III

c. Many possible answers, including

O O

NH2 OCH3
OCH3 NH2
d. The imidazole V is much more basic than the pyrrole IV. Protonation of the imidazole at
the unmethylated nitrogen results in better resonance in the conjugate acid than was
present in the conjugate base. No such enhancement of resonance is possible in IV (in
fact, resonance that is present in the neutral compound is lost on protonation at nitrogen,
which means that pyrrole actually protonates preferentially at carbon).
CH3 CH3
N N

N N
H H

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 2024 USNCO Part 2 Solutions

e. Since reaction with bromine takes place at carbon, the additional N in the imidazole V is
electron-withdrawing and deactivating, since its lone pair is in the plane of the ring and
so cannot stabilize the cationic intermediate in the reaction. In contrast, the lone pair of
the nitrogen on pyrrole is stabilizing to the intermediate:
CH3 Br
N Br

CH3 CH3
CH3
N –HBr N
Br Br
+ Br2 N

H
CH3
N
or polybrominated
products also OK
CH3
N Br Br

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