Annotated Solution for USNCO National Exam 2022 Part I

Author: Luke Chen

Proofreader: Dr. Qiang “Steven” Chen
Updated on July 15, 2022

Question 1: Difficulty: Medium

The first step to any stoichiometry problem is to write the balanced chemical equation. In this case, Learning Objectives:

Sr(s) + 2NH3(l) = Sr(NH2)2(s) + H2(g). We are given that Sr is the limiting reagent, and we can stoichiometry

calculate that 0.125 g / 87.62 g·mol-1 = 0.00143 mol Sr reacts. By the balanced chemical equation (1
mole Sr reacts to form 1 mol H2) we get that 0.00143 moles of H2 are produced. B is the answer.
If you are not sure about what is strontium amide, you may still figure out the stochiometric ratio of
Sr and H2 by knowing that each Sr loses two electrons during the reaction. Moreover, the amide here
is the conjugate base (NH2–) of ammonia, which is different from the amide (-C(=O)–NH-) in organic
chemistry.

Question 2: Difficulty: Hard

One strategy for this question is to go through each answer choice and verify the % arsenic by mass. Learning Objectives:
mass percent and empirical
A) %As = (1×74.92) / (12.01 + 3 + 74.92 + 14.01) × 100% = 72.1%.
formula; paramagnetic vs
B) %As = (1×74.92) / (12.01×2 + 6 + 74.92) = 71.4%.
diamagnetic; prediction of
C) %As = (2×74.92) / (12.01×2 + 6 + 74.92×2 + 14.01×2) = 72.1%
unpaired electron(s)
D) %As = (2×74.92) / (12.01×4 + 12 + 74.92×2) = 71.4%
We are between B and D for the correct answer, and it comes down to whether each compound is para
or diamagnetic. Typically, MO theory is preferred for issues of magnetism, but since each of these
compounds is relatively complex, we will use Lewis structures instead. Drawing the Lewis structure
of each molecule, we notice that 3 unbonded electrons are found on the central As in the Lewis
structure for C2H6As. This means that one unpaired electron exists in compound B and B is
paramagnetic. No radical electrons exist on compound D. D is thus our answer since it has the
right %As and is also diamagnetic. You may interpret C4H12As2 as the dimer of C2H6As, which pair
the single electron on As through the dimerization.
The compound C4H12As2 is actually called cacodyl, or tetramethyldiarsine with the structure and
geometry shown below.

Source: Wikipedia
2 / Annotated Solution for USNCO National Exam 2022 – Part I

Difficulty: Medium Question 3:

Learning Objectives: Let us go through each answer choice.
stoichiometry; limiting
A) A seems reasonable. When only 1.00 g of Fe was added, the graph is still upward sloping meaning
reactant; graph reading
adding more Fe would increase product yield. This implies that Br 2 is still present in the system and
Fe is limiting.
B) From the graph, we can easily see that 10.6 g product is obtained when 2.00 g of Fe is added. If
1 mol Fe 1 mol FeBr2
FeBr2 is the product, let’s check the stoichiometry, 2.00 g Fe × × ×
55.85 g 1 mol Fe

(55.85+77.90×2) g
1 mol FeBr2
= 7.72 g. This is not 10.6 g, thus answer choice B is incorrect. The product is actually

FeBr3, which is reasonable as Br2 is a strong oxidant and oxidizes Fe(s) to a higher oxidation state.
C) Looking at the graph, when 2.50 g of Fe are added, this is already well into the flat region of the
graph (the vertex exists when 2.00 g of Fe are added). The flat region means that adding additional Fe
here will not produce any more product because no more bromine is left to react (Br 2 is the limiting
reagent). Adding any more Fe past 2.00 g will be in excess, thus an excess 0.50 g Fe exists when 2.50
g Fe is added. C is incorrect.
D) Once again looking at the graph, 3.50 g added Fe also is in the flat region where Br2 is the limiting
reagent. D is clearly incorrect.
A is thus our answer.
Note: The chemical equation is Fe(s) + 3/2 Br2(l) = FeBr3(s).

Difficulty: Medium Question 4:

Learning Objectives: We know the masses of Cu2S and CuS in the ore must add to 89.0 g. We also know that there must be
stoichiometry; mixture
in total 67.5 g / 63.55 g·mol-1 = 1.06 moles of copper total between Cu2S and CuS. Calling the moles
analysis
of Cu2S x and the moles of CuS y, we can set up the following system of equations.
2x + y = 1.06 (balancing the number of moles of copper)
(63.55×2 + 32.07)x + (63.55 + 32.07)y = 89.0 (balancing mass)
Solving the system gives us y = 0.290 mol of CuS, multiplying that by the molar mass of (63.55+32.0)
g·mol-1 gives us 27.7 g of CuS, approximately B.
You may set up the mass of each compound and use the Cu% in each to obtain a similar system of
equations.

Difficulty: Medium Question 5:

Learning Objectives: This is a simple stoichiometry problem, although it may look complicated. We know that there are
solution stoichiometry
0.02123 L × 0.0235 M = 4.98×10–4 mol S2O32– added. Since I3– and S2O32– react in a 1:2 ratio (by the
2nd equation), we know that there must be 4.98×10–4 /2 = 2.49 × 10–4 mol I3–. Now looking at the first
equation, 1 mol of I3– forms when 1 mol OCl– reacts. Thus, the 2.49×10–4 mol OCl– react and are
present in the bleach sample. To find the concentration of hypochlorite, we divide 2.49×10–4 by the
volume of 0.0750 to get a concentration of 0.00332 M, or C.
 Annotated Solution for USNCO National Exam 2022 – Part I / 3

Question 6: Difficulty: Medium

This question tests your understanding of colligative properties. The boiling point elevation is directly Learning Objectives:
colligative properties of
proportional to the number of particles in solution. We can rank the boiling points of each aqueous
solutions; dissociation of
solution by taking the product of the salt concentration and the number of ions formed per formula
strong and weak
unit of salt dissolving. electrolytes
A. 0.10 × 4 ions (3 Na+ and 1 PO43–) = 0.40
B. 0.30 × 3 ions (2 Na+ and 1 HPO42–) = 0.90
C. 0.50 × 2 ions (1 Na+ and 1 H2PO4–) = 1.00
D. 0.70 × appx. 1 “particle” (H3PO4 does not fully ionize) = 0.70
Though H3PO4 is triprotic, even the first dissociation is very limited as indicated by a small Ka1 value,
similarly, the dissociation of HPO42– and H2PO4– is more negligible.
C forms the greatest number of particles and thus C has the highest boiling point.
(For those wanting the mathematical explanation, ΔT=imKb. i represents the number of ions formed
per formula unit of salt, m is the molality of the salt, and K b is a constant that depends on the solvent
identity. Kb is constant for all the answer choices since the solvent is water for all trials. We can
approximate molality using molarity for a dilute aqueous solution since 1 L of solution typically uses
very close to 1 kg of solvent.)

Question 7: Difficulty: Easy

Flame test colors for IA and IIA metals should be memorized. Al does not have a clear flame test, B Learning Objectives:
flame test
is green typically, Na is bright yellow, and Sr is red. D is our answer.

Question 8: Difficulty: Medium

A) Chlorine is more reactive than Bromine and thus the Br2 cannot reduce and displace Cl–. Looking Learning Objectives:
description chemistry /
at a reduction potential table, indeed Cl 2 has a more positive reduction potential than Br2. No reaction
reactions, color of
and thus no color change occurs.
ions/gases
B) The chemical reaction that occurs is CO32–(aq) + 2H+(aq) = H2O(l) + CO2(g). None of the reactants
or products are colored, thus no color change occurs.
C) A complexation reaction occurs 3C2O42–(aq) + Fe3+(aq) = [Fe(C2O4)3]3–(aq). Complex ion reactions
often involve color changes. Even if you didn’t know that trioxalatoferrate(III) is green (compared to
the yellow Fe3+ ion in the reactants and colorless oxalate ion), you could guess C is the correct answer.
D) No reaction occurs for this answer choice and no color change occurs. Note that Co 2+ is a pink ion
in solution.

Question 9: Difficulty: Medium

Three elements are known to form protective oxide coatings: Al, Si, and Cr. A is aluminum and the Learning Objectives:
properties of metals
correct answer. We can eliminate the other answer choices since B) and D) are alkaline earth metals
and oxidize to form oxides in air, which further reacts with water and CO2 from the air, and C) is iron
which is known to rust by oxidizing in air (in the presence of water).
4 / Annotated Solution for USNCO National Exam 2022 – Part I

Difficulty: Medium Question 10:

Learning Objectives: Determining the number of components in a mixture is best done by chromatography. Boiling point
colligative properties of
determination does not tell us the number of compounds in a mixture if the boiling points of the
solutions; dissociation of
components are relative close. Combustion analysis is typically used to identify the empirical formula
strong and weak
electrolytes of a sample, this will not tell us the number of compounds in a mixture. In this case, nail polish remover
consists of many volatile organic compounds, such as acetone. Since they vaporize at low temperatures,
gas chromatography is preferred to paper chromatography (works best for non–volatile and colored
species such as dyes). A is the answer.

Difficulty: Hard Question 11:

Learning Objectives: Knowing solubility rules, we can eliminate A and D since alkaline earth metal sulfides tend to be
solubility rules; HSAB
soluble. If you are familiar with the cation qualitative separation scheme, you know that CdS
theory
precipitates out in acidic conditions while MnS only precipitates out once base is added. C
You may use hard-soft acid-base (HSAB) theory to get a more detailed understanding of this problem.
Here the annotation to a similar problem in Local 2018 (Q8) is quoted with minor revision for your
reference:
According to hard-soft acid-base theory (HSAB), hard acids bind strongly with hard bases, soft acids
bind strongly with soft bases. The order of the hardness of the four cations from hard to soft is Ba2+ >
Ca2+ > Mn2+ > Cd2+, as higher charged and smaller sized cations are harder Lewis acids; more
electronegative, lower charged, and smaller sized anions are harder Lewis bases. S2–, less
electronegative, larger in size, is a typical soft base, which binds strongly with soft acids and binds
weakly with hard acids. So CdS, a soft acid-soft base combination, has the strongest binding affinity
and the lowest solubility in water. Therefore, CdS is the only sulfide precipitate here which is not
soluble even in strong acids.
In general, metal sulfide precipitates tend to be more soluble in acid as the formation of the weak
electrolyte H2S, indicated by MS(s) + 2H+(aq) → M2+(aq) + H2S(aq). So, if the precipitate has a
smaller Ksp (less soluble), it is harder to dissolve in both water and in acid.

Difficulty: Hard Question 12:

Learning Objectives: Let us write a skeleton equation for the reaction: M(s) + H2SO4(aq) = MSO4(aq) + H2(g). The
laboratory and error
collection of gas over water is an essential laboratory technique. A reaction occurs in a water through
analysis; ideal gas law;
such that the gasses produced are collected in a flask or graduated cylinder. Their volume is determined
partial pressure of water
vapor
and, by using the ideal gas law, the number of moles of gas produced can be calculated. P(H2) for the
ideal gas law is calculated by subtracting the vapor pressure of water from the atmospheric pressure.
Checking each answer choice:
A) This will cause no effect. Firstly, if you accurately take into account the new concentration of
sulfuric acid your calculations still should be accurate. Secondly, the reaction likely will occur with
sulfuric acid in excess, so the number of moles of sulfuric acid truly does not matter for the calculation.
 Annotated Solution for USNCO National Exam 2022 – Part I / 5

B) Since M is oxidized in the reaction, replacing some M with its already oxidized form will effectively
reduce the number of moles of M in the reaction. Less moles of gas will be produced with less M
reactant, making the calculated number of moles of M also decrease. Since the mass of “M” (including
the oxide) is weighed to be the same, the molar mass will be too high. B is the answer.
C) This makes the pressure in the ideal gas law artificially high; since pressure is directly proportional
to moles, the number of moles of H2 calculated will also be artificially high. By the balanced equation,
this also makes the calculated number of moles of M too high while keeping the measured mass of M
the same. This makes the calculated molar mass of M too low.
D) The vapor pressure must be subtracted from the atmospheric pressure to find P(H2) used in the
ideal gas law; not subtracting the vapor pressure will make P(H2) artificially high. Just like in answer
choice C, this results in a too high calculated number of moles of M, making the calculated molar mass
too low.

Question 13: Difficulty: Medium

A) Using the Ideal Gas Law, we can find the initial moles of Ar as 1.0 L × 1.00 atm ÷ (0.08206 L atm Learning Objectives:
ideal gas law; partial
/ mol K × 298 K) = 0.0409 mol and the initial moles of Kr as 2.0 L × 0.5 atm ÷ (0.08206 L atm / mol
pressure; average speed of
K × 298 K) = 0.0409 mol. We know the total volume of the system with the open stopcock is 1.0 +
gas molecules
2.0 = 3.0 L, and that the total number of moles is 0.0409 × 2 = 0.0818 mol. Using the ideal gas law,
we can find the final pressure as P = nRT/V = 0.0818 × 0.08206 × 298 / 3.00 = 0.666 atm. This is not
1.00 atm, thus A is incorrect.
B) We calculated that the total number of moles of each gas is equal, thus B seems correct. However,
we must be careful with this answer. We know the moles of Ar and Kr in the whole system are equal,
but we cannot know how these moles are distributed (in the 2.0 L container or the connected 1.0 L
container). B is a trick answer. The number of moles of Ar in the 2.0-L container is supposed to be 2/3
of the total moles of Ar, while the number of moles of Kr in the 1.0-L container is 1/3 of the total
moles of Kr.
C) The average speed is dependent on temperature and molar mass. urms = 3RT/M. Both gasses are at
the same T but have different molar masses, thus their average speed (represented by the root mean
squared velocity, urms) cannot be equal.
D) From our last calculation, we know this is correct. Since P = nRT/V, equal number of moles of each
gas indicate that each gas has the same partial pressure. D is the answer.

Question 14: Difficulty: Medium

Carbon and Bromine have an electronegativity difference, yet it isn’t very much. By Pauling’s Learning Objectives:
analysis of intermolecular
electronegativity scale, Carbon and Bromine differ in electronegativity only by 0.3. Both CH 2Br2 and
forces
CHBr3 are polar molecules, but since the electronegativity difference is slim the charge separation is
also slim. Thus, both molecules do not have strong dipole–dipole interactions. Clearly, hydrogen
bonding does not occur since there is no O–H, F–H, or N–H very polar bond. Additionally, we know
both molecules do not have long range covalent bonds (they are molecular compounds held together
6 / Annotated Solution for USNCO National Exam 2022 – Part I

by intermolecular forces); thus, D does not make sense as an answer. The only valid option is London
Dispersion Force differences, or A. Bromine is a very polarizable atom, and replacing H by Br adds
34 electrons. The electron cloud of CHBr3 is much larger and more polarizable than CH2Br2, thus
London Dispersion Force differences would significantly increase the boiling point of CHBr3
compared to CH2Br2.

Difficulty: Hard Question 15:

Learning Objectives: There are two possibilities for this phase diagram. The slope of the solid–liquid boundary can be either
states of matter; phase
positive or negative.
diagram
A) This is accurate. In either scenario if the pressure is below the Triple Point Pressure, the solid–
liquid line does not extend to this pressure. The only boundary is between solid and gas, thus increasing
the temperature will sublime the solid to a gas. A is the answer.
B) The relative densities of the solid and liquid state depend on the slope of the solid–liquid boundary
line. Whichever state is favored at the higher pressure will be denser. Since we do not know the slope
of the solid–liquid boundary, we cannot identify which state is denser.
C) At 193 K (slightly higher than the triple point temperature), in the bottom figure with a negative
solid–liquid boundary slope, solid is not thermodynamically stable at 193 K. ×However, if the solid–
liquid slope is positive (top diagram), the solid state is thermodynamically stable at high pressure.
Once again, this statement depends on the sign of the slope, which we are not given.
D) This is clearly incorrect. The pressure can be any number and so can the temperature.

Difficulty: Hard Question 16:

Learning Objectives: Intuitive Solution: What affects the volume of a real gas that makes it deviate from ideal nature?
ideal gas law; the deviation
Intermolecular forces and molecular size. Molecular size stays constant; thus, we consider changes in
of real gases
intermolecular force strength when evaluating the answer choices below.
I. When you heat a gas, the gas molecules move more rapidly and escape the attractive intermolecular
forces that tie them closer with other molecules. As a result of the lower intermolecular forces at higher
temperature, the volume of the real gas should more than double when doubling the temperature at
constant pressure. Thus, statement I is correct.
II. When gasses are at high pressure, they collide often with the walls of the container and with each
other. The molecules are packed close together, thus, they experience significant intermolecular forces
with their neighbors. When the gas pressure decreases and the volume expands, once again the gas
molecules are no longer close to each other, and their intermolecular forces decrease. This further
decreases the attraction between the molecules and increases the volume the molecules occupy –
making the volume more than double when pressure is halved. Thus, statement II is correct.
C is thus our answer.
Technical Solution: This question relies on the idea of the compressibility factor for a real gas, Z. The
compressibility factor quantifies a gas’s deviation from ideal nature (ideal gas has Z = 1) and is defined
as Z = PV/nRT. As the graphs below show, Z typically decreases with increasing pressure when P is
 Annotated Solution for USNCO National Exam 2022 – Part I / 7

less than ~100 atm and increases with higher temperature. Statement I has an increase in temperature,
meaning Z will decrease during this process. If the gas were ideal, V would double, but since Z
increases, V will increase by more than a factor of 2. Statement I is correct. Statement II has a decrease
in pressure with a very small P (far left of the top graph), thus this will increase Z. In this case V will
increase by more than a factor of two. Statement II is also correct; thus, C is the correct answer.

[Source: Lumen Learning]

Source: Chemistry Stack Exchange

Question 17: Difficulty: Hard

This problem is typical and challenging in the recent years of USNCO, which is about the best Learning Objectives:
melting point of mixtures
explanation of an unexpected experimental result. An equimolar mixture of C 6H6 and C6F6 melts
sharply at 23.7 °C, which is higher than the melting points of both. Choice A and C can be easily
eliminated, the two reasonable explanations are (B) C6H6 and C6F6 form a crystal containing equal
amounts of the two substances, and (D) The enthalpy of mixing of C6H6 and C6F6 is negative. If the
mixing is exothermic, which means the interaction between C6H6 and C6F6 is stronger than that among
C6H6 molecules and that among C6F6 molecules, the mixture is expected to melt at a higher
temperature. However, this explanation can’t explain the keyword “sharply”, as it is a mixture which
8 / Annotated Solution for USNCO National Exam 2022 – Part I

typically has a melting range rather than a sharp melting point, thus, D is not the best explanation.
Let’s check out B, if C6H6 and C6F6 form a crystal, which is a new compound with a stronger
interaction, the melting point is expected to be higher and sharp. If we go further to think about why
and how the two compounds can form a crystal, we may realize that benzene is electron–rich with the
delocalized pi system, while C6F6 is electron–deficient as the six more electronegative fluorines attract
the electrons from the benzene ring, making it positive. So, it is reasonable to predict the two ring
structures can stack together to form an adduct through the electrostatic interaction in a 1:1 molar ratio.
Thus, the correct answer is B.
The above analysis is also confirmed by the reference: Williams, J. H.; Cockcroft, J. K.; Fitch, A. N.
Angew. Chem., Int. Ed. 1992, 31, 1655. A diagram is shown below for the readers to get a better
understanding.

Source: Peer Kirsch, Modern Fluoroorganic Chemistry – Synthesis, Reactivity, Applications

Second, Completely Revised and Enlarged Edition

Difficulty: Easy Question 18:

Learning Objectives: A nearest neighbor in a crystal structure is simply the atoms most closely surrounding another atom.
solid models; coordination
In the case of atoms of type C (edge center), they are most closely surrounded by 2 atoms of B in a
number
linear fashion (the B atoms are directly adjacent to C on either side of it). Other A and C atoms are
further away. As a result, A is the answer.

Difficulty: Medium Question 19:

Learning Objectives: heat I) Work is defined as – external pressure times change in volume. w = –PΔV. By definition, if the
and work; entropy and
volume of the balloon changes by deflation, work is done by the surroundings (nitrogen) on the system
temperature
(balloon). This is the case because ΔV is negative, making work positive (positive work is work done
on the system). Statement I is correct.
II) Entropy for a gas increases as temperature increases because the molecules of the gas are more
disordered (thermal entropy). When the balloon is immersed in very cold liquid nitrogen, heat will
flow away from the balloon and into the nitrogen surroundings. The nitrogen will heat up as a result,
making nitrogen’s entropy increase. Statement II is correct.
Thus, C is the correct answer.
 Annotated Solution for USNCO National Exam 2022 – Part I / 9

Question 20: Difficulty: Hard

Assume we have 1 L = 1000 g of water. For the heat of the water to increase by 1.0 degree Celsius Learning Objectives:
calorimetry; pH calculation
(from 25.0 to 26.0 ℃), q = mcΔT = 1000 g × 4.18 J / g ℃ × 1.0 ℃ = 4180 J. (We assume the mass
of the solution does not change since its density and volume remain constant). The dissolution of KOH
provides this heat. Each mole of KOH dissolving releases 57600 J, thus we need 4180/57600 = 0.0726
moles of KOH. The concentration of OH– at the final state is 0.0726 mol / 1 L = 0.0726 M. pOH = –
log[OH–] = 1.14. pH = 14 – pOH = 12.9. D

Question 21: Difficulty: Medium

Write the reaction of the formation of ClF3 (g): 3/2F2(g) + 1/2Cl2(g) = ClF3(g) Learning Objectives:
concepts of enthalpy of
ΔHof = –158.9 kJ/mol
formation and Gibbs free
ΔSof = Som[ClF3(g)] –1/2 Som[Cl2(g)] – 3/2 Som[F2(g)]
energy of formation;
= 281.6 – 1/2×223.1 – 3/2×202.8 Hess’s law; ΔG = ΔH –
= –134.15 J/molK TΔS
ΔGo f = ΔHof –TΔSo f = –158.9 × 1000 J – 298 K × (–134.15) J / mol K
= –118900 J/mol = –118.9 kJ/mol
C

Question 22: Difficulty: Hard

At the triple point, the liquid and vapor phases are in equilibrium. Learning Objectives: ΔGo
= –RTlnK = ΔHo –TΔSo;
Br2(l) ⇌ Br2(g)
ΔGo vs ΔG
ΔGovap = –RTlnK = –RTlnP[Br2(g)] = –8.314 × 265.9 × ln(0.058) = 6300 J/mol
ΔGovap = 6300 J/mol = ΔHovap – TΔSovap =ΔHovap – 265.9×89.0
ΔHovap = 30.0 kJ/mol
D
Note: A common misconception for this problem is to interpret the ΔGovap = 0 at 265.9 K and 0.058
bar as the liquid and vapor phases are in equilibrium, then a wrong value of ΔHovap = TΔSovap =
265.9×89.0 = 23.7 kJ/mol, is obtained. Please be aware the difference between ΔGo and ΔG. At
equilibrium state, ΔG = 0, however, ΔGo is not necessary to be 0 unless the equilibrium constant K =
1. Back to this problem, 0.058 bar is not standard pressure, in another word, the equilibrium
temperature of the liquid and vapor phases at standard state (1 bar) is NOT 265.9 K. So, another way
to solve this problem is to combine Clausius-Clapeyron equation with the normal boiling point Tb and
ΔGo = ΔHo – TΔSo = 0 at standard state, as shown below.
o
1 bar ∆𝐻vap 1 1
ln =− ×( − )
0.058 bar 8.314 𝑇b 265.9
o − 𝑇 ∆𝑆 o = ∆𝐻 o − 𝑇 × 89.0 = ∆𝐺 o = 0
∆𝐻vap b vap vap b vap

Solving the system of equations gives us the same results of ΔHovap = 30.0 kJ/mol, as well as Tb =
337.1 K.
10 / Annotated Solution for USNCO National Exam 2022 – Part I

Difficulty: Hard Question 23:

Learning Objectives: This question is fundamentally one about intermolecular forces. Straight chain alkanes only are held
intermolecular forces;
together by London forces, while primary alcohols are held together by London forces as well as
hydrogen bonding; entropy
dipole interactions and hydrogen–bonding. In general, permanent dipole and hydrogen–bonding
change of vaporization
interactions are stronger than London forces – breaking these strong, stabilizing interactions during
the vaporization process heavily increases the system disorder, thus the standard entropy of
vaporization of alcohols is expected to be consistently higher than those of alkanes of the same molar
mass. Furthermore, the alcohol is still expected to have an upward (positive) slope, since its London
forces will increase when the molar mass increases, similar to the alkane – thus causing more “stability”
to be lost when vaporizing. A is the graph best fitting these deductions.
Extension: Another interesting fact to point out is that the gap between the two trend lines is getting
larger as the molar mass increases. How to explain that?
For short chain alcohols, each individual molecule can align in many different orientations since the
overall interactions in the liquid are dominated by hydrogen bonding. However, in longer chain
alcohols, in the liquid form the molecules tend to arrange all in the same direction with the hydrophobic
hydrocarbon region on one side and the hydrogen bonding alcohol groups on the other side. This
additional order that is removed when the liquid vaporizes will increase the ΔSvap of the longer chain
alcohols in comparison to simply the alkanes. This explains why the gap between the two lines
increases as molar mass increases.
[Note: A common mistake on this problem is a misapplication of Trouton’s Rule, which states that the
standard molar entropy of vaporization of liquids is always around 88 J/mol K. However, this does
not apply to hydrogen bonding liquids – a heavy limitation that prevents its application for alcohols].

Difficulty: Hard Question 24:

Learning Objectives: The graph is based on the concept of van’t Hoff equation, which states that ln(K2/K1)= –(ΔHorxn/R)×
van’t Hoff equation; Ksp vs
(1/T2 – 1/T1). This can be rewritten as
molar solubility;
o
Δ𝐻rxn 1
interpretation of graphs ln(𝐾) = − × ( ) + 𝐶 (1)
𝑅 𝑇

with C being a constant. The x–axis of the graph does show 1/T, however the y axis shows ln(molar
solubility) instead of ln(K). In NaIO3, there are two ions formed. The Ksp expression would thus be Ksp
= [Na+][IO3–] or S2 by mass balance. Thus, K is the square of the molar solubility. Taking the ln of
both sides, we get that ln(Ksp) = ln(S2) = 2ln(S) by exponent rules. We can thus rewrite expression (1)
as
o
Δ𝐻rxn 1
2ln(𝑆) = − × (𝑇) + 𝐶
𝑅

o
Δ𝐻rxn 1
ln(𝑆) = − × ( ) + 𝐶′ (2)
2𝑅 𝑇

We now know that the slope between ln(S) and 1/T is –(ΔHorxn/2R). Since the slope given to us is –
2088, we multiply this by –2R = –2(8.314) to get ΔHorxn to be equal to 34720 J/mol, or D.
 Annotated Solution for USNCO National Exam 2022 – Part I / 11

Question 25: Difficulty: Medium

This question requires logical thinking. Let us call the actinium isotope A, the beta decay product B, Learning Objectives:
nuclear decay kinetics;
and the electron capture product E. Note that nuclear decays are first ordered processes.
half-life; kinetics of
A → B + e– k1 = ln(2)/t1/2 = 0.693/35.4 d = 0.0196 day–1
parallel processes
A + e– → E k2 = ln(2)/t1/2 = 0.693/173 d = 0.00401 day–1
The rate constants sum for the overall rate of A’s decomposition. This is intuitive but is also supported
with proof. As a result, the overall rate constant ktotal for A’s decomposition is 0.0196 + 0.00401 day–
1= 0.0236 day–1. The overall half-life is t1/2 = ln(2)/ktotal = 0.693/0.236 day–1 = 29.4 d. A.
Intuitively this makes sense. The half-life of the overall decomposition of A must be smaller than the
half-lives of each individual nuclear reaction.

Question 26: Difficulty: Easy

This is a classic differential rate law question. Between trials 1 and 2, [NO 2] is kept constant while Learning Objectives:
reaction order; initial rate
[CO] doubles. However, the initial rate does not change implying 0 th order rate dependence on [CO].
method for rate law
Between trials 2 and 3, [CO] is kept constant while [NO2] triples (pay attention to the exponents). The
initial rate increases by a factor of 9, or 32, implying 2nd order dependence on [NO2]. The overall rate
law must be Rate = k[NO2]2. B.

Question 27: Difficulty: Medium

This is a fundamental conceptual question. The activation energy is the energy required in a molecular Learning Objectives:
concepts of activation
collision for a reaction to occur and progress to the transition state.
energy, transition state,
A. This is the opposite. Catalysts decrease the activation energy by providing a different mechanism.
intermediate; energy
The decrease in activation energy allows catalysts to speed up reaction rates. profile of reactions
B. Activation energy does not depend on temperature. Temperature changes increase or decrease the
probability a collision exceeds the activation energy barrier but will not change the barrier itself.
C. This is the correct answer. However, if you did not know this fact previously, the process of
elimination is the best way to decide the correct answer. The overall activation energy of a process is
determined based on the energy difference from the highest transition state and the reactants.
Intermediates, almost always higher in energy than the reactants will never be higher in energy than
the highest transition state (remember intermediates are local minima on a reaction coordinate while
transition states are local maxima). Thus, the reactant is closer in energy to the intermediate than the
highest transition state, making the energy change for the formation of an intermediate less than the
activation energy of the process.
D. Clearly this does not make sense. Very few reactions have negative activation energies, but many
exothermic reactions exist (with positive activation energies).
12 / Annotated Solution for USNCO National Exam 2022 – Part I

Source: LibreTexts

Difficulty: Easy Question 28:

Learning Objectives: The fading of crystal violet experiment is a common AP chemistry lab. This question relies on the
fading of crystal violet;
knowledge that crystal violet is colored (violet, as you would expect) and sodium hydroxide is
pseudo kinetics analysis;
colorless.
integrated rate law
I. This is correct. As the crystal violet reacts the violet color should disappear. A linear slope between
ln(absorbance) and time implies first order dependence on crystal violet, the colored species in
solution. The presence of excess NaOH ensures the concentration of NaOH doesn’t change with time,
which is crucial for pseudo kinetic analysis.
II. This is incorrect. The experiment never varied the concentration of hydroxide and measured how
the hydroxide concentration affected the rate law.
A is the correct answer.

Difficulty: Medium Question 29:

Learning Objectives: The wording of the question is confusing, but essentially it asks, “which reaction diagram has the
energy profile of reactions;
reaction reach equilibrium the fastest.” We can immediately eliminate C and D. These two
activation energy;
mechanisms have high activation energies and thus their reactions would go slowly. Deciding between
equilibrium positions
A and B is trickier. In mechanism A, the equilibrium heavily favors P due to the strongly exergonic
ΔGo. The concentration of P at equilibrium state would be very high. On the contrary, mechanism B
does not have very high concentrations of products as ΔGo is barely negative. This, paired with the
important fact that both reactions, regardless of equilibrium position, proceed at the same rate since
their activation energies are the same, indicates B as the mechanism that would reach equilibrium
first. Another way to interpret this is the similar activation energies of forward and backward reaction
in choice B, which implies a faster rate to reach equilibrium.
This concept is similar to that of kinetic vs thermodynamic control of reactions. Only thermodynamics
(ΔGo) governs where equilibrium lies, and only kinetics (activation energy) governs the reaction
rate. I encourage you to research more on this.
 Annotated Solution for USNCO National Exam 2022 – Part I / 13

Question 30: Difficulty: Hard

By inspection of the graph, we identify that increasing [B] increases the initial rate significantly when Learning Objectives: rate
law derivation of
[B] is low, but barely any when [B] is high. This should remind you of enzyme kinetics (Michaelis–
complication reactions
Menten), the rate increases with the concentration of the substrate when the substrate is low in
using steady-state
concentration, while it levels off when the concentration gets higher as all binding sites of the enzyme approximation;
are occupied by the excess substrate. We expect that the rate law of this mechanism will not be linear, interpretation of graphs
but instead be in a form similar to Rate = k[B]/C+[B], C is a constant here. (This equation has linear
dependence of Rate and [B] when [B] is low but no dependence on [B] when [B] is high). We then
proceed through the answer choices and write rate laws consistent with each proposed mechanism.
A) First, let us write out the balanced equations.
A⇌I (k1, k–1)
I+B→P (k2)
Rate = d[P]/dt = k2[I][B]
Using steady state approximation for intermediate I,
d[I]/dt = k1[A] –k–1[I] – k2[I][B]
𝑘1 [A]
[I] =
𝑘−1 + 𝑘2 [B]
𝑘1 𝑘2 [A][B]
Rate = 𝑑[P]/𝑑𝑡 =
𝑘−1 + 𝑘2 [B]
Since [A] is a constant, we notice that this mechanism DOES follow the skeleton rate law we proposed
above. Changes in [B] only affect the rate at low concentrations of [B]. A is the correct answer.
B)
A⇌I (k1, k–1)
I + 2B → P (k2)
d[P]/dt = k2[B]2[I]
Using steady state approximation for intermediate I,
d[I]/dt = k1[A] – k–1[I] – k2[I][B]2
𝑘1 [A]
[I] =
𝑘−1 + 𝑘2 [B]2
𝑘1 𝑘2 [A][B]2
Rate = 𝑑[P]/𝑑𝑡 =
𝑘−1 + 𝑘2 [B]2
Unlike answer choice A, this rate law would not produce the desired graph. This graph would have a
region of concave up (quadratic) dependence of rate on [B] when [B] is low; the graph shown in the
problem appears linear and not quadratic at low [B] concentrations.
C)
B⇌I (k1, k–1)
I+A→P (k2)
d[P]/dt = k2[A][I]
Using steady state approximation for intermediate I,
d[I]/dt = k1[B] – k–1[I] – k2[I][A] = 0
14 / Annotated Solution for USNCO National Exam 2022 – Part I

[I] = k1[B]/k–1 + k2[A]

𝑘1 [B]
[I] =
𝑘−1 + 𝑘2 [A]
𝑘1 𝑘2 [A][B]
Rate = 𝑑[P]/𝑑𝑡 = 𝑘−1 +𝑘2[A]

This has the proto Michaelis–Menten relationship for [A], whereas the graph shows such a relationship
for [B].
D) D has the same problem as C)

Intuitively, without deriving the rate law for each choice, we can see that the function of B in choice
A is more similar to that of the substrate in the enzyme kinetics, in another words, rate increases with
[B] when [B] is small but will be limited by [I] when [B] is getting high.

Difficulty: Medium Question 31:

Learning Objectives: K Firstly, by Dalton’s law we know that if the mixture is equimolar there exists 1.00 bar of both CO and
calculation with the RICE
H2. Addition of the catalyst is irrelevant to the equilibrium position. We then set up an RICE table.
table method

R CO + 2 H2 ⇌ CH3OH

I 1.00 bar 1.00 bar 0

C –x –2x +x

E 1.00–x 1.00–2x x

Total pressure = 1.29 bar = 1.00 – x + 1.00 – 2x + x = 2.00 – 2x → x = 0.355 bar

Kp = x(1.00–2x)2/(1.00–x) = 0.355 × 0.2902 / 0.645 = 6.54. B

Difficulty: Medium Question 32:

Learning Objectives: acid The first step is to use the data given to calculate Ka.
ionization equilibrium; Ka
Ka = [H+][A–]/[HA] = (0.038 × 0.10)2 /(0.10 – 0.038×0.10) = 1.5×10–4.
of acids, percent ionization
We then use this Ka for the new concentration of acid.
Ka = 1.5×10–4 = [H+][A–]/[HA] = x2 / (0.50–x) ≈ x2 / 0.50 → x = 0.0087 (<5% of 0.50, assumption
valid)
%I = 0.0087/0.50×100% = 1.7% A
Moreover, the calculation result is consistent with the Le Chatelier prediction, diluting the solution of
a weak acid shifts the ionization equilibrium to the right side. In another words, the more diluted the
weak acid is, the higher the degree of ionization is.
 Annotated Solution for USNCO National Exam 2022 – Part I / 15

Question 33: Difficulty: Medium

The key point of this problem is that adding a significant volume of sodium chromate will dilute both Learning Objectives: Ksp
and solubility
itself and the barium solution.
Let V be the added chromate volume.
Ksp = 1.2×10–10 = [Ba2+][CrO42–] = [1.5×10–5 M × 1.0 L/(1.0 + V)]2
(1.5×10–5 M × 1.0 L) / (1.0 + V) = 1.10×10–5
1.0 + V = 0.73
A negative V does not make sense. This implies that regardless of the volume of chromate you add,
the concentrations of chromate and barium are never enough to induce precipitation. The issue is the
concentration of the chromate solution added is too dilute. D

Question 34: Difficulty: Medium

I. We know by Le Chatelier’s principle that if Keq increases with increasing temperature, the reaction Learning Objectives: sign
analysis of ΔGo, ΔHo and
must be endothermic. Statement I is incorrect.
ΔSo
II. This statement requires math to verify. Since ΔGo = –RTln(K), ΔGo = –8.314×300×ln(0.020) =
9800 J. ΔGo is positive meaning the reaction is nonspontaneous. We know that ΔHo is also positive
contributing to the positive ΔGo. We cannot say the sign of ΔSo without knowing specifically the
magnitude of ΔHo. ΔHo could be slightly positive and require a strong negative entropy term to make
the reaction have its respective ΔGo or be very positive and ΔS may end up being positive and counter
the magnitude of ΔHo. Statement II is incorrect.
D is the correct answer.

Question 35: Difficulty: Hard

Let us write the net equation: Learning Objectives:

multiple equilibria;
AgCl + 2 HCN ⇌ Ag(CN)2– + 2H+ + Cl–, K = Ksp × Kf × Ka2 = 6.8×10–7
calculation with the RICE
Then apply the RICE table method to set up the equation:
table method
–
R AgCl + 2 HCN ⇌ Ag(CN)2 + 2 H+ + Cl–

I 0.010 mol n mol 0 0 0

C –0.020 + 0.010 + 0.020 + 0.010

E n–0.020 0.010 M 0.020 M 0.010 M

Note: the volume of the final solution of the system above is 1.00 L.
6.8×10–7 = 0.010× (0.020)2 × (0.010) / (n–0.020)2
→ n = 0.26 mol.
C
16 / Annotated Solution for USNCO National Exam 2022 – Part I

Difficulty: Hard Question 36:

Learning Objectives: For this problem, assume each molecular structure represents 1 mol of gas and the initial volume is
LCP; shift of equilibrium
1.0 L.
at constant pressure
Firstly, in order for the total pressure to be kept constant while additional moles of gas are added, the
volume of the container must increase. We eliminate A and B as their volumes remain constant.
Secondly, we must recognize that the equilibrium mixture still must have ratios of NO 2 and N2O4 that
follow K. In this case, let us use Kc. Our initial mixture contains 4 moles of NO2 and 4 moles of N2O4.
In the 1 L container, each gas has a molarity of 4 M. Because the balanced equation for the
dimerization is 2NO2 ⇌ N2O4, K = (4)/(42) = 0.25. The correct answer must have a ratio of
[N2O4]/[NO2]2 consistent with this. In C, 4 moles of each gas are present, however the volume doubles
and the concentration of each gas is 2.0 M. K = (2)/(22) = 0.5. This is incorrect. In D, 6 moles of NO2
are present and 3 moles of N2O4. The concentrations are thus 3 M NO2 and 1.5 M N2O4. K = (1.5)/(32)
= 0.25. D is the correct answer.
We may apply the Le Chatelier Principle to get the answer without quantitative analysis. As some
noble gas is added to a constant pressure system, the “net” pressure of the reactants and products
actually decreases as the total pressure including the partial pressure of the noble gas keeps constant.
According to LCP, the equilibrium will shifts to the decomposition side to produce more gas molecules
(more NO2(g) ), which can reduce the pressure decrease. The only correct choice with more NO2 (less
N2O4) is D.

Difficulty: Easy Question 37:

Learning Objectives: In A), P is in the +5 oxidation state. In B), Mn is in the +6 oxidation state. In C), S is in the +4 oxidation
oxidation states
state. In D), N is in the +5 oxidation state. B is the answer.

Difficulty: Easy Question 38:

Learning Objectives: Write and balance the half reactions.
balance redox equations
5 × (H2C2O4 → 2CO2 + 2H+ + 2e–)
using half-reaction method
2 × (5e– + 8H+ + MnO4– → Mn2+ + 4H2O)
The coefficient of H2O is 8. D

Difficulty: Medium Question 39:

Learning Objectives: mol e– =0.153 A × 16400 s / (96500 C/mol e–) = 0.0260 mol
electrolysis and Faraday’s
2 moles of electrons are required to deposit 1 mol of Cu and 3 moles of electrons for 1 mol of Rh.
law
We write two equations, 1 to balance the moles of electrons and 1 to balance mass. Let x be the moles
of Cu and y be the moles of Rh.
2x + 3y = 0.0260
63.55x + 102.91y = 0.826
Solving the system of equations, we get x = 0.0130, y = 0. Thus, we know the metal is only copper. A
 Annotated Solution for USNCO National Exam 2022 – Part I / 17

Question 40: Difficulty: Hard

Firstly, calculate ΔHo and ΔSo. Learning Objectives: ΔGo

= ΔHo – TΔSo = –nFEo;
ΔHo = –153.89 – 2×55.19 + 2×61.84 = –140.59 kJ/mol
dependence of ΔGo and Eo
ΔSo = –112.1 + 42.6 + 2×111.3 – 2×115.5 – 41.6 = –119.5 J/mol×K
on temperature
Calculate ΔGo from the above values
ΔGo = ΔHo – TΔSo = –140.5 + 119.5×298/1000 = –105 kJ/mol
I. Eo = –ΔGo/nF = 105000/(2×96500) = 0.544 V=0.54 V. Correct
II. Since ΔSo is negative, increasing the temperature will make ΔGo more positive due to the expression
ΔGo = ΔHo – TΔSo. ΔGo becoming more positive will make the cell potential more negative, since =
–ΔGo/nF (n and F are kept constant). Incorrect.
The answer is thus A.
However, the equation provided in the problem is actually not balanced, there is a coefficient of 2
missed for Ag in the product side. This issue won’t affect the calculation of ΔHo as the standard
enthalpy of formation of Ag(s) is 0, but it will affect the ΔSo value, thus further affect ΔGo and Eo.
Thus, statement I actually is incorrect, and correct answer is D if the equation is balanced.
Note: both A and D are accepted. You may further realize how important it is to balance the equation
for any equilibrium or stoichiometry problem.

Question 41: Difficulty: Hard

Let us write the balanced equations: Learning Objectives:

multiple equilibria; Eo =
Ni + 2Ag+ → 2Ag + Ni2+ (x)
RTln(K)/nF
For this expression, ΔGo = –nFEo = –2×96500×1.05 = –203000 J/mol = –RTlnKx = –8.314×298×ln(Kx)
Kx =3 .33×1035
Ni2+ + 4 CN– → Ni(CN)42– (y)
Ag+ + 2 CN– → Ag(CN)2– (z)
(x + y – 2×z) Ni + 2Ag(CN)2– → 2Ag + Ni(CN)42– K = Kx × Ky / Kz2
K = 3.33×1035 × 2.0×1031 / (9.8×1021)2 = 6.94 × 1022
Eo = RTln(K)/nF = 8.314×298ln(6.94×1022)/(2×96500) = 0.68 V.
A

Question 42: Difficulty: Medium

The key principle in this question is that reduction potentials are intensive properties, which are not Learning Objectives:
Hess’s law; calculating the
summable (not a state function). Note: Calculating the cell potential using the reduction potential of
potential of a redox couple
the cathode to subtract that of the anode doesn’t mean potentials are summable, as cell potential
from two related couples
actually is the potential difference between the cathode and the anode. So, in order to relate the desired
half reaction with the provided half reactions, we need to convert to ΔGo first.
ΔGo1 = –nFEo1 = –4×96500×0.74 = –286000 J/mol
ΔGo2 = –nFEo2 = –2×96500×1.15 = –221950 J/mol
18 / Annotated Solution for USNCO National Exam 2022 – Part I

The desired equation is a sum of the first and second equations; ΔGo is a state function and thus its
values can be summed.
ΔGo3 =ΔGo1 + ΔGo2 = –507950 = –nFEo = –6×96500×Eo3
Eo3 = 0.88 V
A

Difficulty: Easy Question 43:

Learning Objectives:
Using the Aufbau principle, the electron configuration for Ni is 1s22s22p63s23p64s23d8. The 4s
electron configuration of
electrons are lost first when ionizing, thus Ni 2+ has the electron configuration 1s22s22p63s23p63d8. D
atoms/ions at ground state

Question 44 was omitted from the exam.

Difficulty: Medium Question 45:

Learning Objectives:
B is the answer. It can be interpreted in the following manner: Br 2 and I2 have atoms with very large
trends of bond strength
covalent radii. Their bonds will be very long and as a result will be very weak. Their bond dissociation
down a group; uniqueness
of the 2nd period elements enthalpies will be very low. Using this logic, you may deduce F–F would have the highest bond
enthalpy. However, all these halogen molecules have 3 lone pairs on each of the two atoms. In F–F,
these three lone pairs surround very small F atoms and exist very close to each other due to the short
F–F bond. There is significant repulsion as a result; this repulsion destabilizes and weakens the F–F
bond. Cl is large enough to not experience very high repulsion due to lone pairs yet is not large enough
to make the covalent bond ridiculously long either.
Generally, for main group elements, the bonds get weaker down the group, however, the second period
elements are typical exceptional due to their much smaller sizes. So, this is a typical example of the
uniqueness of the second period elements.

Difficulty: Medium Question 46:

Learning Objectives: When looking at the orbital structures, adding an electron to a group 1 element will add to the valence
periodic trends and
s orbital and pair with the existing s electron. Adding an electron to a group 2 element must add to a
exceptions; electron
higher energy p orbital. As a result, adding an electron to a group 2 element will release less energy
affinity
due to the orbital it adds in. B
Another choice which also looks correct is C, more energy is released by the group 2 elements because
they have more protons in the nucleus. Recall the first ionization energies (IE1) of elements across a
period, taking the second period as an example, the general trend is increasing, however, there are two
elements which are lower in IE1 than the previous element, B (group 3) and O (group 6). Taking the
2p1 electron from B needs less energy (IE1 of B), which means adding one electron to the 2p orbital
of Be releases less energy (electron affinity of Be). Similar trends also occur in other periods. Thus,
we can eliminate C. In summary, though the trends in electron affinity is not as regular as the IE1, we
can expect group 2 and group 5 elements to have lower electron affinity (releasing less energy or even
absorbing energy).
 Annotated Solution for USNCO National Exam 2022 – Part I / 19

Source: Wikipedia (left) and Pearson (right)

Question 47: Difficulty: Medium

If two orbitals have the same shape and orientation, by definition they must have the same values of l Learning Objectives:
meaning and values of
and ml, since l governs the orbital shape (s, p, d, f) and ml the orientation. The different number of
quantum numbers; radial
nodes must be radial nodes (cannot be angular nodes, since l is the same), which depends on the
and angular nodes of
number of principal shells there are (specifically, the n.) n thus will vary. A is the correct answer. orbitals
(Alternative solution: the total number of nodes is defined as n – 1, thus if the number of nodes differ
n must differ)
Here we provide a good website to help you visualize the shape and nodes of each orbital. A node of
the orbital is generally the place with an electron probability of 0. Taking the 3p orbital for example,
as shown below, there is one radial node (a spherical surface) and one angular node (a nodal plane
here). As indicated by the name, radial nodes are related to the radius, the distance to the nucleus,
while angular nodes are related to the angular part of the orbital (wavefunction), which are typically
planes.

Source: Quara
20 / Annotated Solution for USNCO National Exam 2022 – Part I

You may need to review the meaning and value of each quantum number by doing some homework,
either check the local exam annotation or do some googling.

Difficulty: Easy Question 48:

Learning Objectives: We are familiar that the Balmer series containing all electron transitions to the n = 2 energy level (n =
Bohr’s model and
k → n = 2, k > 2) corresponds to visible light emission and that the Lyman series containing all electron
Hydrogen’s emission
transitions to the n = 1 energy level (n = k → n = 1) corresponds to UV light emission. Similarly, in
spectrum; Rydberg’s
equation order to absorb visible light, the electron will be initially present in the n = 2 energy level and then get
excited to a higher state. In order for the atom to emit a UV photon, the electron must subsequently
fall to the n = 1 energy level. B is the answer that follows these principles.
You may mathematically confirm the above series using the Rydberg’s formula for hydrogen atoms,
as shown below:
1 1 1
∆𝐸 ∝ = −𝑅H × ( 2 − 2 )
𝜆 𝑛f 𝑛i
where the nf and ni represents the final and initial energy level, and RH = 1.10×107 m-1 is the Rydberg’s
constant.

Difficulty: Medium Question 49:

Learning Objectives: Drawing Lewis structures is the key to solve this problem.
Lewis structures and
A) HCNO has one resonance structure with a triple bond between C and N and another with double
resonances; bond length
bonds between C=N and N=O. The triple bond resonance structure is more favorable since the – formal
charge is on oxygen, the most electronegative element.
B) HNCO has one resonance structure with a triple bond between N and C but a much more stable
resonance form with 0 formal charge when there is a double bond between N=C and also C=O (lone
pair on N).
C) H3CNO is most stable with a lone pair on nitrogen and a double bond between N=O. There may
only be a single bond between C and N since C already has three bonds to hydrogen and can only form
1 more bond without expanding its octet.
D) Similar to above, C can only form a single bond with N since C cannot exceed 4 bonds.
HCNO

major minor

HNCO

minor major
 Annotated Solution for USNCO National Exam 2022 – Part I / 21

When comparing these molecules, we can eliminate C and D which have C–N single bonds. A and B
both have two resonance forms: one with a CN double bond and one with a triple bond. However, in
structure A the triple bond resonance is more stable by formal charge and thus contributes more to the
overall molecular structure. As a result of A having more triple bond character between C and N, it is
expected that A will have the shortest C–N bond length.

Question 50: Bonding, Medium Difficulty: Medium

Draw the Lewis structure to begin. Learning Objectives:

Lewis structures;
molecular geometry;
VSEPR model

The electron cloud geometry of this molecule (5 electron domains) is trigonal bipyramidal, as shown
above in the right. One F is located in the equatorial plane with the 2 lone pairs and the other two Fs
are located above and below the plane in axial positions. (the more repulsive lone pairs both
preferentially occupy equatorial positions to avoid destabilizing 90 degree interactions with axial
pairs)
I. This statement is incorrect. Looking at the Lewis structure above, two of the F–Cl–F bond angles
are 90 degrees, however the bond angle between the two axial Fs is 180 degrees.
II. In trigonal bipyramidal electron pair geometry, the axial and equatorial bond lengths are not equal.
The 3c–4e type bonding of axial bonds makes the axial bonds longer. As a result, the Cl–F bond
lengths are not all equal. D is the correct answer.

Question 51: Difficulty: Medium

This question is very easy to tackle if you are familiar Learning Objectives:
concepts of isoelectronics;
with MO theory. Isoelectronic to O2, the NF MO
molecular orbital diagram
diagram is very similar to that of O2, except that the
atomic orbitals of F is lower in energy than N as F is
more electronegative. (This fact does not affect the
correct answer, however). Seeing the attached MO
diagram, there are two electrons in the π*2p molecular
orbitals, which by Hund’s law will each occupy
separate orbitals. There are 2 unpaired electrons,
making C the correct answer.

Source: Student Solutions Manual for

Whitten/Davis/Peck/Stanley's Chemistry, 9th edition
22 / Annotated Solution for USNCO National Exam 2022 – Part I

Difficulty: Hard Question 52:

Learning Objectives: This question again relies on molecular orbital theory. When drawing out the MO diagram of NF, the
molecular orbital diagram;
HOMO (Highest Occupied Molecular Orbitals) containing the highest energy electrons (π*2p) is an
ionization energy
antibonding orbital. By definition, antibonding orbitals are higher in energy than both atoms that form
comparison based on the
MO diagram it (N and F). Ionizing an electron from a higher energy orbital would require LESS added energy as
the energy is already at a more excited state and needs less energy to overcome the nuclear attraction.
As a result, the correct answer for the ionization energy of NF must be less than the ionization energy
of N and also F. In this case, A is the only answer that fits this criterion.
Moreover, as predicted by the molecular orbital diagram above, the IE of NF is closer to that of N.

Difficulty: Hard Question 53:

Learning Objectives: To approach this question, first draw out the Lewis structure for guanidinium. We have 4 + (5+1+1)×3
Lewis structures and
– 1 = 24 electrons. Subtracting 9×2 for 9 single bonds, we get 6 electrons left. In order for every atom
resonances; deviation of
to have an octet, we draw two N atoms with lone pairs and the third N atom with a double bond to the
VSEPR model
central C. This is only one resonance structure, however. Any of the nitrogens can be the one with the
double bond, leading to two more resonance structures. What is important to realize is that the
existence of a partial π bond involving each of the N atoms means that each N atom must have a 2p
orbital available for π bonding. As a result, each N atom cannot fully sp 3 hybridize, as then it would
lose the ability to π bond. Since each N atom is now sp 2 hybridized, they each must be trigonal planar
in geometry as sp2 hybridization dictates. A is the correct answer.

Source: Semantic Scholar

One more resonance can be drawn with each nitrogen single bonded to the central carbon, which
carries a positive formal charge. This is a minor resonance as the central carbon disobeys the octet
rule, which is much worse than the three resonances above, and it won’t affect our analysis.
In summary, when there are delocalized involved (indicated by multiple resonances), the geometry
and hybridization may be different from the results predicted by the VSEPR mode.

Difficulty: Hard Question 54:

Learning Objectives: This question relies on crystal field theory. Firstly, it is important to understand that the absorption of
crystal field theory and d-d
visible light of transition metal complexes typically occurs by d–d transition, or the energy required
transition; strengths of
to promote one d electron from a lower d orbital energy level to a higher energy level. This energy,
ligands and splitting
energy; E = hf / λ called splitting energy, is determined based on three factors 1) coordination geometry, 2) metal charge,
3) ligand strength. What you can notice is that each molecule listed has cobalt in the same oxidation
state of +3. Additionally, all of the complexes have 6 bonding pairs and are in the octahedral geometry.
Thus, the splitting energy is dependent only on ligand strength. Since we are looking for the complex
 Annotated Solution for USNCO National Exam 2022 – Part I / 23

ion that absorbs the longest wavelength and we know that energy of light is inversely proportional to
its wavelength, we are looking for the ligand that will induce the smallest splitting energy. By the
spectrochemical series, we know that halogens such as F– are some of the weakest field ligands and
thus would induce a very low splitting energy. All of the other ligands are strong field ligands and
would induce a high splitting energy and absorb short wavelengths for d–d transition. Thus, the fluoro
complex C is our answer.

Source: Stack Exchange

You may not need to memorize the whole spectrochemical series, but you’d better know some general
trends, such as, halides are weak ligands with small splitting energy, while CN– and CO with carbon
as the donor are strong ligands with large splitting energy and nitrogen containing ligands are
something in between.

Question 55: Difficulty: Hard

For drawing isomer questions, the strategy is four fold: 1) determine the degree of hydrogen Learning Objectives:
isomer counting; types of
unsaturation (also commonly called double bond equivalence) to determine the possible functional
isomers
groups (functional isomers), 2) draw all possible carbon skeletons (chain isomers), 3) add functional
groups to different positions (positional isomers), 4) look for stereoisomers, especially enantiomers.
1. Unsaturation degree = 2(#C)+2 – #H – #Cl = 2(3) + 2 – 6 – 2 = 0. This means that all carbons
are saturated, and no rings or double bonds are present. So the molecule is a chloroalkane.
2. For a 3 carbon backbone with no rings, only one skeleton exists. A “linear” 3 carbon chain
(propane) without branches.
3. Functional groups (Cl atoms) can be added in the following manners. Make sure to count all
locations, especially when two Cls attach to the same carbon atom.

4. Going through each constitutional isomer, we realize that since there are no double bonds or
rings, no cis–trans isomerism will exist. We then search for enantiomers. 1,1–dichloropropane,
24 / Annotated Solution for USNCO National Exam 2022 – Part I

1,3–dichloropropane, and 2,2–dichloropropane are achiral. Carbon 2 of 1,2–dichloropropane

is chiral as C2 connects to four different groups or the structure lacks a mirror plane. As a
result, 1,2–dichloropropane exists as two enantiomers. This makes a total of 5 structures; B
is our answer.

Question 56:
Difficulty: Hard A nitrile is a compound in the form R–CN. Sodium cyanide is a good nucleophile and the DMSO
Learning Objectives: SN2 solvent (polar aprotic) signals to us that this reaction likely is S N2 (bimolecular nucleophilic
reactions
substitution). We know SN2 requires an electrophile with a good leaving group attached to a saturated
carbon. Going through the answer choices.
A) No leaving groups (or really any functional groups) at all are present here. This is a very unreactive
compound.
B) The alcohol group is reactive but will not undergo SN2 unless it is made into a better leaving group
in the first place. This will not produce a nitrile.
C) The double bond (a weak nucleophile) indicates electrophilic addition, but as the cyanide anion
itself is a nucleophile, no reaction will occur here. We are looking for SN2.
D) This is the best answer. We have a bromine (good leaving group) attached to a saturated, primary
carbon. SN2 will occur rapidly here with the cyanide attacking the carbon and displacing bromine to
form a nitrile. D is the correct answer.

Difficulty: Hard Question 57:

Learning Objectives: The molecular orbital diagram for the pi bonds of a conjugated diene can be made by drawing p orbitals
molecular orbital diagram
on each carbon atom with different orientations. The lowest energy MO is made when the diagram
of conjugated dienes
has no nodes (all p orbitals have the same orientation), the second lowest when there is 1 node (there
is one plane at which the two p orbitals directly adjacent to it have opposite orientations), etc. For 1,3–
butadiene, there are 4 carbon atoms and thus 4 p–orbitals drawn in each MO. 4 MO configurations
exist: one with 0 nodes, one with 1 node, one with 2 nodes, and one with 3 nodes (be aware that for
four p–orbitals, there can only be 3 “transitions” between p–orbital orientation for adjacent orbitals,
thus 3 nodal planes). Each MO, like an atomic orbital, can fit 2 pi bonding electrons. Since there are
2 pi bonds and thus 4 pi bonding electrons, the two MOs with the least amount of energy (0 nodes and
1 node) are occupied (2 and 3 node MOs are empty). Looking at the answer choices, I has 2 nodes and
II has 1 node. Thus, only MO II is filled, making B the correct answer.
Readers may draw the other two anti-bonding MOs for practice.
 Annotated Solution for USNCO National Exam 2022 – Part I / 25

Question 58:
The reaction hinted here is acetal hydrolysis. Acetals consist of two ether groups attached to the same Difficulty: Hard

carbon atom, which is the product of the dehydration of aldehyde/ketone with two molecules of Learning Objectives:
hydrolysis of acetals;
alcohols (or a diol). An acetal can be hydrolyzed and yield back the aldehyde/ketone ONLY under
comparison of acetals and
acidic conditions. Thus, an acetal is a protecting group used to protect a carbonyl group from reacting
hemiacetals
under neutral or basic conditions, which can be further deprotected under acidic condition.

Source: Chemistry Steps

Under basic conditions, the alkoxide is a bad leaving group and will not leave from the acetal to reform
a carbonyl, thus acetals can’t react with water to hydrolyze under basic condition. Now we are looking
for an acetal in the answer choices. B is the correct answer here. It is easy to see the methoxide as
an ether, yet the other functional group attached to the top carbon is also an ether, albeit intramolecular.
Reacting B with acid and water will yield an aldehyde. None of the others react exclusively with water
under acidic conditions. Hemiacetals (D) can decompose to the carbonyl under both acidic and basic
conditions – under basic conditions the hydroxyl group can get deprotonated by the base, then the lone
pair on the negative charged oxygen goes down, forms a double bond to reform the carbonyl and force
the alkoxide to leave.
Choice A is an ether, which is much more stable than the acetals and hemiacetals. Note: ethers can
hydrolyze under acidic condition but less readily.
Readers may try to draw the product (aldehyde) of the hydrolysis of B under acidic conditions as a
practice.
26 / Annotated Solution for USNCO National Exam 2022 – Part I

Difficulty: Medium Question 59:

Learning Objectives: IR The simplest way to get this question right is through memorization. A sharp IR signal around 1700
spectrum; IR absorption of
cm–1 is characteristic of a carbonyl group. This matches answer choice C. It is more difficult to derive
common functional groups
this answer from the formula for wavenumber relating force constant and reduced mass. Ethers (A, B)
have signals in the fingerprint region (<1500 cm –1), alkenes (A, B) have weak signals around 2200
cm–1, and alcohols (D) have strong and broad signals above 3000 cm –1 induced by the hydrogen
bonded O–H bonds.

Difficulty: Hard Question 60:

Learning Objectives: Any changes to the chemical structure of a protein can change its function, thus any of the options
reduction of disulfide
could satisfy the criteria of deactivating insulin. The true question is which of the following organic
bonds
processes requires the use of a mild reducing agent? In organic reactions, reduction typically involves
addition of hydrogen/hydride.
A) Cleaving a disulfide bridge into two thiol (R–SH) groups clearly requires a reducing agent. Two
hydrogen atoms are added to cleave the bond.
B) Cleaving peptide bonds into a carboxylic acid and an amine is a hydrolysis reaction, not a reduction.
Water instead of hydrogen is added.
C) Any substitution occurring at an alcohol group would not be a reduction. The only way to reduce
an alcohol group would be to remove the functional group completely, a synthesis that would require
more than a “mild” reducing agent.
D) Reducing agents may decrease overall charge, yet they are typically balanced with proton transfers
that nullify net charge changes. Overall, this is a weak answer as the main reason proteins change in
functionality is a change in functional groups and thus structure.
A is the correct answer.