Annotated Solution

2019 USNCO National Exam Part I

Author: Alec Zhu
Proofreaders: Dr. Qiang ‘Steven’ Chen, Aaron Oong
Editors: Dr. Qiang ‘Steven’ Chen and Aaron Oong
Updated on April 7, 2021

Solutions

1. n = m/M w , where n is number of moles, m is the mass, and M w is the molecular weight. Applying this
calculation to all the options gives us choice B .

2. The stoichiometric ratio is one mole of oxygen for two moles of hydrogen, or 16 g : 2 g to form 18 g (0.50
mol) of product. Option A fits this, and B and C have a limiting reagent. Option D has more of both
reactants than the amounts needed to make 18 g, so it’s D .

3. One mole of troegerite has 2 × 3 + 4 × 2 + 12 = 26 moles of oxygen.

(N A is Avogadro’s number)
       
1.00 g 26 mol O 23 −1 1.00 g 26 mol O
N A× × = 6.022×10 mol × × = 1.20×1022
Mw 1 mol troegerite 1304.0 g/mol 1 mol troegerite

i.e. C .

4. Since we are told Hünig’s base is monobasic, it is not a daring assumption to say it probably only has
one nitrogen atom (organic bases are amines, in which one, two or three hydrogens in NH3 are replaced
by alkyl groups, R). If we assume there are 100.0 g of base, we get 14.82 g of H and 10.84 g of N, i.e.
14.82 mol of H and 0.7737 mol of N, so a mole ratio of 19:1. A quick calculation of the moles of carbon
confirms that this is a real molecule. Hence, it’s D .

5. Let x be the number of moles of MgO, and y be the number of moles of Mg3 N2 . Thus, since each mole of
the nitride has 3 moles of magnesium, the total number of moles of magnesium in the sample is x + 3y.
We started off with 1.000 g of Mg, i.e. 41.14 mmol of Mg, so we have the following equations:
x + 3y = 0.04114 mol
40.31x + 100.95y = 1.584 g (the sum of the masses of the nitride
and the oxide is the mass of the final sample).
Solving gives x = 0.02998 mol and y = 0.003721 mol, so 3y = 0.01116 mol of Mg is in the nitride form.
Hence, 0.01116/0.04114 = 27.13% is in the nitride form; C .

6. This is a very acidic solution, so the dissociation of CH3 COOH is basically zilch. We really only need to
look at the number of moles of HNO3 and HCl; each mole of acid contributes one mole of H+ since both
acids are strong. n(H+ ) = (45.0 mL)(0.10 M) + (50.0 mL)(0.20 M) = 0.0145 mol. The total volume is
45.0 mL + 50.0 mL + 55.0 mL = 0.145 L. So, the overall concentration of H+ is about 0.10 M, pH =
1.00, so C .

7. Hydrated Cu2+ (aq) is well-known to be blue. So, it’s C .

Note: Na2 S2 O4 is a colorless solution, K2 CrO4 is yellow, and Zn(OH)2 is a white precipitate.

1
 8. KNO3 and Ba(NO3 )2 are both neutral as they are made by a strong acid and a strong base. NH4 + is
an acid, and so is Fe3+ , as shown by the following equations:

NH4 + (aq) + H2 O )
−−
−* +
− NH3 (aq) + H3 O (aq)
3+ −−* 2+ +
Fe(H2 O)6 (aq) + H2 O ) −− Fe(H2 O)5 (OH) (aq) + H3 O (aq)

Strongly charged metal ions like Fe3+ , Al3+ or Cr3+ are often acidic, because their aquo complexes
readily lose H+ :
M(H2 O)6 x+ −−→ M(OH)(H2 O)5 (x−1)+ + H+
It is helpful to know the approximate pKa s of various acids. Ammonia, and similar amines, are decently
strong bases, so their conjugate acids are quite weak, with pKa s of between 9 and 10. The aquo complexes
of strongly charged metal ions can be quite acidic, with pKa s between 3 and 7. Of course, the higher
the charge density the stronger the acid. Thus, it’s D .

9. The purpose of a reflux is to allow a reaction to take place at a high temperature in a certain solvent,
i.e. the boiling point, without the solvent simply boiling away. To achieve this, a condenser is used to
cool the solvent vapors so that they turn back into a liquid, so that the solvent doesn’t boil away. If
the solvent were to boil away, it would be a waste of solvent, the solvent would need to be replenished,
and if the solvent boils to dryness the temperature will spike and lead to bad things as the temperature
exceeds the boiling point.
• In setup A, there is a hole meant for attaching a vacuum line, obviously having a hole for solvent
vapor to escape defeats the point (there needs to be an opening at the top of the condenser, but
ideally vapor cannot escape the condenser as it is cooling down and condenses).
• C has a similar issue as A.
• D is an improper use of a volumetric flask, which usually aren’t meant to withstand the high heat.
Besides, the surface area of the liquid is miniscule compared to the volume, which means the boiling
liquid will be confined, potentially causing an explosion. Certainly, it will be very violent.
• Setup B is the proper one, with the Erlenmeyer flask providing a safe vessel to contain boiling
solvent and vapors.

Hence, it’s B .

10. The relevant reaction is:

AgX + 2 NH3 −−→ [Ag(NH3 )2 ]2+ + X− , where X is a counterion, typically is a halide.

This reaction will proceed if the Keq of the dissolution reaction above is greater than one. It is not too
hard to imagine that if AgX has a smaller Ksp , the Keq of the dissolution will be smaller (note that the
Keq of dissolution is equal to Kf × Ksp , where Kf is the formation constant for [Ag(NH3 )2 ]+ .) Thus, it is
sensible to choose the salt AgX with the lowest Ksp , so that it does not dissolve in ammonia. Ag+ is very
soft (lower in charge, larger in size, and less electronegative), so we should pick a very soft counterion,
i.e. iodide, so the answer is C .

AgI is also pretty yellowish. Note that [Ag(S2 O3 )2 ]3 – has a much larger Kf than [Ag(NH3 )2 ]+ since
S in S2 O3 2 – is softer than N, so AgI is still soluble in thiosulfate. Also, AgF and Ag(CH3 COO) are
water soluble, so you only need to pick between AgI and AgCl.

If you are confused by the ”hard and soft acid/base” here, you may refer to the annotated solution
of Q8 in local 2018. Actually even if you are not sure about the solubility difference of AgX in
ammonia and thiosulfate, you may also eliminate AgCl using its color.

11. Titration is useless if the molar mass is unknown, and besides, the impurities might also react with
NaOH. Combustion only gives elemental analysis, and is useless to assess the purity of unknown impure
compounds. UV-vis is similarly unhelpful, since we have no idea what functional groups should be present
in the compound that might absorb UV-vis light. Melting point is useful, since it does not require the
melting point to be known. A pure substance will usually display a clear melting point, melting uniformly
at a single temperature. An impure substance will exhibit a lower, more broad melting point. Hence,
A.
2
12. • Error A with some Na2 CO3 used in the standardization spilled will result in less Na2 CO3 being
used in the standardization, so less HCl solution will be used. This will mean the concentration of
HCl will appear to be higher because of the reduced volume. Since the concentration of HCl will
appear to be higher than it actually is, the concentration of ammonia will also appear higher, so A
is correct.
• If error B is committed, NH3 is being removed from the titration flask with the paper towel, so less
HCl will be used, and the amount of ammonia will appear lower (it’s better to just swirl the flask,
or use magnetic stirring, and further use deionized water to rinse the buret tip and inner wall of
the flask to make sure that all titrant added is reacted with the analyte).
• If error C is committed, NH3 will be partially neutralized by CO2 in the air, thus its concentration
is lower than the actual one.
• Error D should not change the results, since shifting the pH curve up and down does not change
where the sharp change occurs.
The answer is A .

13. Metals don’t dissolve in CCl4 (a nonpolar solvent), and they don’t dissolve in water (some metals do react
with water, but this is arguably not dissolution, rather a chemical process). Metals are also conductive
at pretty much all temperatures. Thus, the answer should be A . Don’t be off put by the low melting
point; some metals have quite low melting points such as alkali metals with few valence electrons. By
the way, D describes a semiconductor like silicon.

14. I2 is quite nonpolar, and would preferentially dissolve in the dense, nonpolar CCl4 . CCl4 does not mix
with polar water. So, we see a deep violet layer containing I2 beneath a colorless aqueous layer (I don’t
think it would be perfectly colorless; dissolved iodine in water is usually pale yellow). Thus, it’s C .

15. CH2 – CH2 has weak IMFs and can be immediately eliminated. As the rest of the choices have similar
molar masses, it is as simple as considering which compound is capable of forming the most hydrogen
bonds. Hydrazine (H2 NNH2 ), with 2 lone pairs on nitrogens (hydrogen bond acceptors) and 4 N – H
bonds (H as the hydrogen bond donors) that are able to engage in hydrogen bonding, is the clear winner.
B.

16. As the container expands, liquid pentane will enter the vapor phase, and the pressure will be maintained
at the saturated vapor pressure until all the pentane becomes a gas, at which point the pressure will
drop as there is no more liquid pentane to vaporize to fill the expanding container. This is the behavior
seen in chart C. A quick calculation confirms that there is not enough pentane to fill an 8.0 L container
at the vapor pressure, so D is incorrect. Answer is C .

mRT
pV = nRT =
M
In order to fit the 8.0 L conainer with a saturated vapor pressure of 620 mmHg,
pV M 620 × 8.0 × 72.15
m(minimum) = = = 18.9 g > 10.0 g
RT 62.36 × (273 + 30)

17. HBr reacts with CH3 NH2 when the vapors meet in the middle of the tube to form a salt, which is
observed as a white ring of [CH3 NH3 + ]Br – . Since HBr has a high molecular weight, it diffuses slowly,
so the methylamine diffuses further, and the white ring appears closer to the HBr side. It’s A .

You may read Graham’s effusion law for further quantitative analysis.

3
18.
m mass of unit cell
ρ= =
V volume of unit cell
In the fcc lattice, each unit cell has 4 metal atoms (8 atoms in the corner ×1/8 + 6 atoms in the face
centers ×1/2 = 4), as shown below:

source: Callister & Rethwisch 5e

Thus,
4 × Mw (metal)
ρ= , where a is the edge length of the unit cell (cube).
NA a3
It is convenient to convert a to cm (1 pm = 10−10 cm) as density of solids is commonly expressed as
g/cm3 . We obtain

ρa3 NA 12.45 × (380.3 × 10−10 × 6.02 × 1023 )

Mw (metal) = = = 103 g/mol
4 4

i.e. Rh, C .

By the way, you could probably guess the answer to this. 12 g/cm3 is pretty dense, much denser than
light potassium (which floats on water). The first row transition metals like vanadium usually have
moderate densities, about 5 g/cm3 . Only the second and third row transition metals are really dense
(especially third row).

Please be aware that the Z in the parenthesis is the atomic number, not the relative atomic mass.

19. The freezing of water forms more structured hydrogen bonds between the water molecules. The formation
of stronger IMFs in the solid phase means this process is exothermic. Or you may easily get the similar
conclusion through thinking that the melting of ice absorbs heat. At low temperatures (below the freezing
point), the freezing of water is favorable, so it’s also spontaneous. A .

20. Only reaction (3) has glucose, so start from there. This reaction produces CO2 ; the only other reaction
that produces CO2 is reaction (2), so reverse reaction (2) and multiply by 2, so that overall the reaction
will produce 2 moles of CO2 . This produces 2 moles of acetic acid, which we deal with by reversing
reaction (1) and multiplying it by 2. Note that we can also come to these conclusions by noting that 2
moles of ethanol will be needed, so we should reverse reaction (1) and double it. Thus, we have:

∆H3 + (−2)∆H2 + (−2)∆H1 = −2805.0 + (−2) × (−874.2) + (−2) × (492.6) = −71.4 kJ/mol A

Actually this is how you apply Hess’s Law to solve problems like this.

21. Note that the dissolution of Li2 CO3 is unfavorable, as Ksp = 0.1752 < 1 (∆G◦ = −RT ln K > 0).
Furthermore, increasing temperature decreases the solubility. In accordance with Le Chatelier’s principle,
we expect an exothermic reaction to shift towards reactants as temperature increases, i.e. decreasing
Ksp . This can also be easily seen from the van’t Hoff equation. Therefore, the dissolution of Li2 CO3
has ∆H ◦ < 0. But since the reaction is unfavorable at 298 K, ∆S ◦ must also be less than 0 as
∆G◦ = ∆H ◦ − T ∆S ◦ . So the answer is D .

By the way, although the dissolution of a salt might appear to be an increase in disorder, the solvation
of ions requires forming tight knit solvation shells, so often ∆S ◦ for dissolution is close to 0 or negative.
4
22. A rigid, well insulated container is an isolated system, which can’t exchange either matter or energy with
the environment. According to the second law of thermodynamics, the entropy of any isolated system
must increase in a spontaneous process, so the answer is C .

Why is it not Gibbs free energy? The short answer is that Gibbs free energy is used for constant
pressure systems, not constant volume systems.

23. (1) Use the equation ∆G = ∆G◦ + RT ln Q; T = 298 K.

(2) First compute
X X
∆G◦ = ∆G◦f (products) − ∆G◦f (reactants)
= [(−394 kJ/mol) + (−604 kJ/mol)] − [(−1129 kJ/mol)]
= 131 kJ/mol

(3)
a(CO2 ) × a(CaO)
Q=
a(CaCO3 )
The activity of any pure liquid or solid a is simply 1. The activity of a gas is simply its pressure.
If you don’t know what activity is, you may just use Q p = P (CO2 ).

(0.4 mbar)(1)
Qp = = 0.0004 bar. You need to convert to bars, since the standard pressure is 1 bar.
(1)

You may see other problems in USNCO use 1 atm as standard pressure, since they are quite close in
value (1 atm = 1.013 bar), but the actual standard pressure is 1 bar according to the latest IUPAC
definition.
∴ ∆G = ∆G◦ + RT ln Q = 131 kJ/mol + 8.314 × 298 × ln(0.0004) = 112 kJ/mol, so it’s B .

24. (1) Note that qrxn = −qcalorimeter .

(2) qcalorimeter = C × ∆T ; where C is the heat capacity.
(3) To find the heat capacity, multiply the mass by the specific heat capacity, and don’t forget the mass
of salt:

C = [10.0 g + 100.0 g] × 4.184 J/g/K = 460.2 J/K

qcalorimeter = C × ∆T = 460.2 J/K × [17.11◦ C − 24.00◦ C] = −3.17 kJ, so qrxn = 3.17 kJ.

(4) We need the molar change in enthalpy, i.e the change in enthalpy per mole. There are 10.0/80.05
= 0.125 mol of NH4 NO3 .
∴ ∆H ◦ = qrxn /n = 3.17/0.125 = 25.4 kJ/mol, i.e. D .

25. The rate is simply the rate of the slow step.

Rateslow step = k[CH3 C(OH)CH3 + ]

Since the first step is fast and reversible, we can assume it is in equilibrium state, and we can use that
to solve for the concentration of the intermediate.
[CH3 C(OH)CH3 + ]
Keq = , so [CH3 C(OH)CH3 + ] = Keq [CH3 COCH3 ][H+ ]
[CH3 COCH3 ][H+ ]

Rateslow step = k[CH3 C(OH)CH3 + ] = kKeq [CH3 COCH3 ][H+ ] = keff [CH3 COCH3 ][H+ ]

i.e. A .

5
26. Use the Arrhenius equation:
   
k2 Ea 1 1
ln =− −
k1 R T2 T1

T1 = 25.0 + 273.15 = 298.2 K, T2 = 35.0 + 273.15 = 308.2 K

k
We know the rate doubles when temperature increases, so k2 = 2
1
Plug and chug: Ea = 52.9 kJ/mol, so A .

Please be aware the R used here must be 8.314 J/mol/K to cancel the unit.

27. (1) Imagine two reactions happening simultaneously:

k
Pinene −−1→ A,
k
Pinene −−2→ B

(2) Rate of consumption of pinene in the first reaction is k1 [Pinene]

Rate of consumption of pinene in the second reaction is k2 [Pinene]
(3) k1 [Pinene] + k2 [Pinene] = (k1 + k2 )[Pinene], the overall rate constant is k1 + k2 . In the example of
the problem, the answer would be 0.22 + 0.13 = 0.35.
So, D .

28. Cl2 (g) + 3 F2 (g) −−→ 2 ClF3 (g), for every 3 mol of F2 consumed, 2 mol of ClF3 is produced. Thus, you
also need to flip a sign.

Therefore, ∆[ClF3 ]/∆t = −(2/3)∆[F2 ]/∆t, so C .

29. A catalyst needs to reduce the activation energy of reaction through altering the reaction path. A and
B don’t reduce the activation energy, so they can’t possibly be the answer. D has an “intermediate”
which is more stable than the product, so the product can’t even form! The correct answer is therefore
C .

30. • A is wrong, since the rate clearly depends on the concentration of azide according to the rate law.
In this case, the concentration of azide is a constant, so the effective rate constant is keff = k[N3 – ];
[N3 – ] has a strong impact on the effective rate constant.
• C is wrong because the reaction is irreversible, so the product I – has essentially no effect on the
reaction.
• D is wrong, since the second order kinetics is compatible with a single elementary step of CH3 I +
N3 – −−→ CH3 N3 + I – .
Therefore, B is correct.

If the initial concentrations of CH3 I and azide are equal, rate = k[CH3 I][N3 – ] = k[CH3 I]2 , so
the rate law changes into second order since [CH3 I] = [N3 – ] all the time during the reaction.
According to the integrated rate law for second order reaction, 1/[CH3 I] = 1/[CH3 I]0 + kt, the
half-life t1/2 = 1/(k[CH3 I]0 ), which means the half-life is reversely proportional to the initial
concentration of [CH3 I], then it takes half as long for [CH3 I] to decrease to 0.005 M as it does for
it to decrease from 0.005 M to 0.0025 M.

31. Ksp = [Pb2+ ][F – ]2 . The concentration of Pb2+ is simply equal to the solubility. Since one mole of
PbF2 has 2 moles of fluoride, the concentration of F – is double the solubility. Plug and chug, you get
Ksp = 4 × (2.1 × 10−3 )2 = 3.7 × 10−8 , so C .

6
32. This is an example of an amphoteric salt, where one ion is a weak base and the other is a weak acid. We
don’t know the concentration of NH3 or CH3 COOH, so it’s impossible to use the Henderson-Hasselbalch
equation. It turns out that in this kind of situation, where the salt is composed of a weak acid with Ka1
and a weak base whose conjugate acid has Ka2 , the pH = (pKa1 + pKa2 )/2 = 7, so C .
The same equation can be applied to calculate the pH of NaHCO3 (aq), which is amphoteric.

But we should derive this equation. Note that strongest base present is acetate (AcO – ), and the
strongest acid present is NH4 + , so the dominant reaction is the reaction of these two species:

AcO− + NH4 + )
−−
−*
− AcOH + NH3

To find H+ , we should use the two Ka expressions:

[H+ ][AcO− ]
= Ka (acetic acid)
[AcOH]
[H+ ][NH3 ]
= Ka (ammonium)
[NH4 + ]
[H+ ][AcO− ] [H+ ][NH3 ] [AcO− ]
   
[NH3 ]
Ka (acetic acid) × Ka (ammonium) = × = [H+ ]2 ×
[AcOH] [NH4 + ] [AcOH] [NH4 + ]
Note that because of our original reaction equation, [AcOH] ≈ [NH3 ], and of course, [AcO – ] ≈
[NH4 + ] since they are in 1:1 ratio in the salt.

[H+ ]2 (1)(1) = Ka1 × Ka2

Taking the log of both sides gives the equation we had earlier.

33. Use RICE diagram:

Reaction P (PCl5 ) P (PCl3 ) P (Cl2 )

Initial 2.7 bar 2.7 bar 0
Change −x +x +x
Equilibrium 2.7 − x 2.7+x +x

x(2.7 + x)
Keq = = 0.015
2.7 − x
x = 0.015 bar

Note that since Keq is small, the reaction won’t go forward much, so P (PCl5 ) and P (PCl3 ) approximately
cancel out. Thus, it’s A .

34. • A is incorrect, because increasing the volume will force the reaction to the side with more particles
by Le Chatlier’s principle, i.e. to the right.
• B is incorrect because increasing the total pressure by adding an inert gas has no effect on the
partial pressures of the relevant species.
• C is incorrect because adding more PCl5 will also shift the reaction to the right.
• D is correct because this reaction is endothermic, so reducing the temperature shifts the reaction
to the left.
The reaction must be endothermic, since although ∆G◦ = −RT ln Kp , is positive (Kp < 1), ∆S ◦ is also
positive, so ∆H ◦ must also be positive. The answer is D .

7
35. Let’s assume the salt has the formula M[SO4 ]n , where n is some number.

Then, we have
Ksp = [M2n+ ][SO4 2− ]n

Taking the log of both sides, we have

log Ksp = log[M2n+ ][SO4 2− ]n

Using our log rules, we have

log[M2n+ ] + n log[SO4 2− ] = log Ksp , or log[M2n+ ] = log Ksp − n log[SO4 2− ]

Hence, the slope is −n. Looking at the graph, we see the slope is −1.5/3.0 = −1/2, so we have M(SO4 )1⁄2 ,
which is the same as M2 SO4 , so A is correct.

36. • In this back titration, some weak base is reacted with a bunch of HCl. The excess HCl is then
neutralized with the strong base. We have 1.00/285.34 = 3.50 mmol of morphine if the pill was
pure, and 50.0×0.1000 = 5.00 mmol of HCl. Since morphine is monobasic, it reacts 1:1 with HCl,
so we have 1.5 mmol of extra HCl. This requires 15.0 mL 0.1000 M NaOH to be back titrated, so
I is wrong.
• At the end point, only the excess HCl was titrated, so the species to determine the acidity is mainly
protonated morphine, BH+ at the end point. This makes the endpoint slightly acidic, so methyl red
with a pH transition range of 4.4 ∼ 6.2 is a good choice. Hence, II is correct. You can calculate
the pH at the endpoint to confirm that it is in the correct pH range. The transition range of the
indicator needs to be within the pH windows, the significant change of the pH the titrant added.
Generally, it’s ok if the pH at the endpoint is within one pH unit of the color change range of the
indicator, so 3.4 to 7.2 would be the acceptable pH range for the endpoint.
B is correct.

Let’s further calculate the pH at the end point, in which BH+ is the major species with a molarity
of (50.0 3.50 mmol
mL + 15.0 mL)
= 0.0538 M

BH+ )
−−
−*
−B+H
+
Ka = 10−8.21
√
[H+ ] = 0.0538 × 10−8.21 = 1.82 × 10−5 , pH = 4.74, perfectly matches the transition range of
the methyl red.

37. We have (0.5 A)(250 s) = 125 C of charge, or 125/F = 125/96500 = 1.3 mmol of electrons to work with.
Ag has a more positive reduction potential than Cu since Ag is less reactive, so Ag will deposit first (if
there was any Cu deposited while Ag+ was still in solution, the Cu would react with Ag+ to form Ag
and Cu2+ ion). Since there are only 1 mmol of Ag+ ions, which consumes only 1 mmol of electrons, 1
mmol of Ag will deposit, and the rest of the electrons will be used to deposit copper. So, C .

You may ask how do we know that Ag is less reactive than Cu. We may get it from life experience
since statues made by Cu are relatively easier to rust with a layer of green copper(II) carbonate
hydroxide, Cu2 CO3 (OH)2 while Ag products are more resistant. We may also analyze the trends
of metal reactivity down the group in IIB, copper, silver, and gold, no doubt, gold is the most
unreactive thus the most stable here, similarly, we can conclude copper is more reactive than
silver.

38. Na is +1, O is −2. 2(+1) + 4(−2) + 2x = 0, x = +3. Drawing the structure of the dithionite ion and
then electron counting gives the same result which is B .

8
39. We see that Ni2+ has a more positive reduction potential than Cd2+ , meaning Ni2+ is a stronger oxidizing
agent than Cd2+ . Thus, the reaction that proceeds is:
Ni2+ + Cd0 −−→ Ni0 + Cd2+
More rigorously, we should use the Nernst equation to determine the spontaneity, but we are at standard
state so we can just look at standard potentials.
• Reduction occurs at nickel, so nickel is the cathode, A is incorrect.
• Cell potential is an entirely thermodynamic quantity, and does not depend on the size of the
electrodes involved, thus C is incorrect.
• Adding Ni2+ to the cathode forces the reaction further to the right by Le Chatelier’s principle (see
the rxn above) so it would increase the potential. You may get the same conclusion by applying
the Nernst equation, D is incorrect.
• B is correct. When Ni2+ is consumed and reduced to Ni0 , K+ needs to be added to balance charges
from the salt bridge.
Thus, the answer is B .
40. You can’t just add the voltages for unbalanced half reactions since reduction potential is NOT a state
function!
It is better to add Gibbs free energies as the target half reaction is the sum of the two half reactions
listed in the table:
(F = Faraday’s constant)
∆G◦total = ∆G◦1 + ∆G◦2
◦
−ntotal F Etotal = −F (n1 E1◦ + n2 E2◦ )
◦ 2(−1.13 V) + 1(−0.26 V)
Etotal =
3
= −0.84 V

So, B .
41. This is, in effect, a concentration cell. In the anode, there is a very low concentration of Ag+ due to the
presence of ammonia to convert most Ag+ into complex Ag(NH3 )2 + :
[Ag(NH3 )2+ ]
= Kf
[Ag+ ][NH3 ]2
0.010
+ = 1.6 × 107
[Ag ] × 0.402
[Ag+ ] = 3.9 × 10−9 M
The cathode has [Ag+ ] = 0.010 M.

The reaction that happens is Ag+ cathode (0.010 M) + Aganode −−→ Agcathode + Ag+ anode (very little). This
makes sense based on Le Chatelier’s principle: the anode has very little Ag+ so it would prefer to oxidize
Ag to make more; the cathode has a lot of Ag+ so it prefers to reduce Ag+ .

Ag+ (aq) + 2 NH3 (aq) −−→ Ag(NH3 )2 + (aq) Kf = 1.6 × 107

[Ag(NH3 )2 + ] + [Ag(NH3 )2 + ]
Kf = =⇒ [Ag ]anode =
[Ag+ ]anode [NH3 ]2 Kf [NH3 ]2
0.010
[Ag+ ]anode =
1.6 × 107 × 0.402
= 3.9 × 10−9 , consistent with the discussion above.
The standard cell potential E ◦ of the above reaction is 0 (nothing is really happening), and we can use
the Nernst equation.
[Ag+ anode ] 3.9 × 10−9
 
◦ RT 0.0592
E=E − ln = 0 − log = 0.38 V
nF [Ag+ cathode ] 1 0.010

Hence, it’s B .

9
42. First, we calculate the E ◦ :
E ◦ = 1.36 V − 1.33 V = 0.03 V
Next, the formula for Keq is:
◦
Keq = e(−∆G/RT ) = e(nF E /RT )

From the equation in the question, we deduce that there are 6 electrons being transferred per reaction,
so n = 6. Plugging in the values into the formula and upon solving, Keq = 1.1 × 103 that is B .

43. You may need to have a clear sense of the four distinct lines in the Hydrogen’s emission spectrum (Balmer
series) and be aware that the wavelength of light is inversely proportional to its energy (E = hν = hc/λ).
You may recognize 656 nm as the red end of the visible spectrum (400 − 700 nm), i.e. the red end of
the Balmer series of transitions. It corresponds to the n = 3 → 2 transition. Recalling the Rydberg
equation, we know that energies are proportional to 1/n2 in a hydrogen atom. Your intuition should
tell you that n = 3 → 1 should have a much shorter wavelength. Thus, the n = 4 → 3 transition is less
energetic than the 3 → 2 transition, and the 4 → 2 transition is more energetic. So the electron in the
n = 4 shell can clearly emit light with a longer or shorter wavelength than 656 nm, but mathematically,
there is no transition from n = 4 → x, x < 4 that has the same energy release as the 3 → 2 transition.
So the answer is D .

44. 2+ ions are generally smaller than 1+ ions unless 2+ ions have many layers of electrons, and ionic radius
increases as you go down the group. This immediately singles out Rb+ as the largest ion and Ca2+ as
the smallest. Sr2+ is smaller than the diagonal K+ , one way to rationalize this is to see that Sr has a
bunch of extra protons because of the presence of the d-block, and the d electrons don’t shield as much
as s and p electrons. This phenomenon is known as the d-block contraction, similar to the 4f contraction
in lanthanide (lanthanide contraction). Thus, it’s C .

45. O and N are actually pretty electronegative because of their small size. However, O is more electronegative
due to the one extra proton in the nucleus. Hence, the correct answer is B .

46. The electron configuration of Ti is 1s2 2s2 2p6 3s2 3p6 4s2 3d2 . Counting the orbitals we have:
1 s + 1 s + 3 p + 1 s + 3 p + 1 s + 2 d = 12 orbitals. There are two partially filled d orbitals in
accordance with Hund’s rule and the answer is B .

47. Write out the nuclear equation:

41 0 – 41
20Ca + – 1e −−→ 19K

• Note that electron capture converts a proton into a neutron, the numbers on the bottom sum the
same for the products and reactants (20 + (−1) = 19) for the charge and the same holds for the
numbers on the top for the mass number. Potassium is not scandium, so I is wrong.
• All nuclear reactions that are favorable must be energetically favorable, so by E = mc2 , the mass
must decrease. The mass that “disappears” gets turned into nuclear binding energy. This question
confused some people in 2019 because free neutrons are slightly heavier than free protons; this
mass difference is of course negligible compared to the nuclear binding energy. So is the mass of an
electron by the way, thus, II is also wrong.

So, D .

48. The extra electron in Al (3s2 3p1 ) when compared to Mg (3s2 ) goes into a 3p orbital. This 3p orbital
experiences partial shielding from the previously filled 3s orbital, which is most consistent with C , since
3s electrons penetrate into the nucleus and 3p electrons don’t. Interestingly, the maximum peak in the
radial distribution function of 3s is further away from the nucleus compared to that in the 3p one.

49. Draw Lewis structures of all these molecules and you’ll see that in SO3 , all the bond dipoles cancel since
it is trigonal planar according to the VSEPR model. Thus, it’s D .

50. CO has a triple bond, which is stronger than the double bond in CO2 . So, A is correct.

10
51. By drawing the Lewis structure of triiodide ion, the central iodine atom in I3 – has 3 lone pairs and is
bonded to two terminal iodine atoms. This is consistent with a trigonal bipyramidal electron domain
geometry. The 3 lone pairs all go in equatorial positions, so the molecule is linear, A .
You may further figure out which atom carries the negative charge.

52. The more oxygens there are, the stronger the electron-withdrawing inductive effect, which can stabilize
the negative charge on the oxygen in the conjugate base of the acid. Additionally, due to resonance, the
negative charge of the ion can be spread over more oxygen atoms. Thus, HBrO4 is the most acidic, so
D.

53. D has the wrong atom connectivity since H on N is not acidic in aqueous solution, and C has the wrong
H – O – N bond angle since it is supposed to be bent due to the existence of two lone pairs on oxygen.
Thus, we have to choose between A and B. The lone pair on the oxygen atom is in resonance with the
other oxygen atoms:

In fact, we can think of all the oxygen atoms being sp2 hybridized. Thus, the molecule is completely
planar. B is the correct answer.

54. Fe(C2 O4 )3 3 – is chiral since there is no mirror plane and inversion center in the structure, see Λ and ∆
isomers, which are mirror image of each other (enantiomers). Looking at the structure, we can see all
iron-oxygen bond lengths are equivalent. Furthermore, there are indeed 6 oxygen iron bonds (this fits
with an octahedral geometry). But we can see that some C – O bonds are closer to single bonds (those
with O bonded to Fe), and some are closer to double bonds. Thus, C is the correct choice.

55. CN – is a good nucleophile, but it is a fairly weak base, so it is more likely to be substitution rather than
elimination. Acetone, being polar aprotic, also helps with SN 2 reactions, Thus, D is correct.

11
56. There are 4 distinct hydrogen chemical environments that can be replaced with chlorines; two primary,
one secondary, and one tertiary. Please be aware that the two – CH3 groups connectd to the same carbon
have the same chemical environments, which means they give the same chlorinated compound. However,
some of the chlorinated compounds are chiral, and exist as pairs of enantiomers. Thus, there are 6
possible compounds including two stereoisomers since two of them have a chiral carbon in the structure,
as shown below, so C .

57. This compound has an HDI (hydrogen deficiency index) of [5 × 2 + 2 − 8]/2 = 2. Since there is one
double bond, there must be one ring (for details, read about hydrogen deficiency index, which is also
called double bond equivalence or degree of unsaturation). So, it’s B .

58. When a C – H bond is broken, a radical is formed (bond strengths usually refer to the homolytic
bond dissociation energy, which is generally much less than the heterolytic bond dissociation energy
for nonpolar bonds). Thus, we want to see which C – H bond should be broken to produce the most
stable radical. Allylic radicals are quite stable due to resonance as shown below, which corresponds to
B.

Note: In a molecule, the position next to an alkene is called allylic.

59. A typical fat (triglyceride) has the following structure:

Note the presence of the three esters. Hydrolysis of these esters in base gives one equivalent of glycerol
(a triol), and three equivalents of fatty acid, but since this is in base, the fatty acids are deprotonated
to give the corresponding salts. (Note that these salts are the main components of old fashioned soaps,
this is why the process is called saponification). Thus, the correct answer is C .

12
60. Just memorize this (or not, I don’t tell you how to live your life).

On a more serious note, it is possible to guess the answer to this one. The cyclic phosphate ester is
much more stable than the phosphate esters of ATP or ADP, so it’s not likely to be used as an energy
source, you may eliminate B, though you might easily connect AMP with ADP/ATP. You should know
that DNA is based on a backbone of the sugar deoxyribose, which lacks an oxygen at the 2 position, so
you may eliminate C and D.

cAMP has an oxygen at the 2 position, so it’s likely to not have much to do with DNA. (In reality,
deoxyribose is derived from ribose, but in a more contrived way).

By process of elimination, A is correct. (Interestingly, 48% of test takers got this right, which is
better than average. This implies people know more biology than chemistry).

13