Annotated Solution

2018 USNCO Local Exam

Authors: Ritvik Teegavarapu and Harys Dalvi
Proofreader and Editor: Dr. Qiang ’Steven’ Chen

Created on November 1st , 2020

Revised on April 7th , 2021

1 Solutions
1. We can use Avogadro’s constant, and then do some dimensional analysis.

1 mol O2 2 mol O 6.02 × 1023 atoms

225 g O2 × × × = 8.47 × 1024 atoms
32.0 g O2 1 mol O2 mol O

Thus, the answer is C .

2. Because the same number of moles must remain before and after dilution, we can set
up the following equation.
M1 V1 = M2 V2
(1.50 M)(V1 ) = (0.300 M)(0.500 L)
(1.50 M)(V1 ) = 0.150 M · L
V1 = 0.100 L
This is 100 mL , or A .

3. We first need to write the reaction in order to perform the stoichiometry. The reaction
is as follows
Cu2 O + H2 −−→ 2 Cu + H2 O
Now we can do the stoichiometry
1 mol Cu 1 mol H2 O 18.00 g H2 O
10.00 g Cu × × × = 1.417 g H2 O
63.55 g Cu 2 mol Cu 1 mol H2 O

Thus, the answer is B .

4. Set a standard amount of enargite at an arbitrary 100.0 g. Thus, there are 48.41 g Cu,
19.02 g As, and 32.57 g S. We can divide by the molar masses of each of the compounds.
1 mol Cu
48.41 g Cu × = 0.7618 mol
63.55 g Cu
1 mol As
19.02 g As × = 0.2539 mol
74.92 g As
1 mol S
32.57 g S × = 1.016 mol
32.06 g S
Dividing by the lowest number, then there will be the ratio of Cu : As : S = 3 : 1 : 4. Thus, the
formula is Cu3 AsS4 , or C .

1
5. We first need to calculate the mass ratio between the calcium nitrate and the calcium.
MCa 40.078 gram
mol
Ca% = = = 0.244
MCa(NO3 )2 164 gram
mol

Thus, for every gram of Ca(NO3 )2 , we will have 0.244 grams of calcium. We additionally know
that we have 1.0 gram of calcium, so we can determine how much calcium nitrate we have
mCa 1.0
mCa(NO3 )2 = = = 4.1
Ca% 0.244

Thus, for 1 gram of calcium, we have 4.1 grams of calcium nitrate to correspond. We can now
determine the mass percent purity by dividing the grams of calcium nitrate by the total mass
4.1
= 82%
5.0

Thus, the answer is D .

6. We can use the formula for the depression in freezing point to solve this question. The
formula is
∆T = i × Kf × m
where i is the van ’t Hoff factor, Kf is the molal depression constant, and m is the molality.
Kf will remain constant and m will be approximately the same since the mass is the same and
the molar masses are comparable, so the dependency of the freezing point will be on the van ’t
Hoff factor.

The definition of the van ’t Hoff factor is the ratio between the actual concentration upon
dissociation of the substance to the concentration based on mass. Thus, we must check what
all of the hydrated salts dissociate into and determine the van ’t Hoff factor for each.

CuSO4 disassociates into Cu2+ and SO4 2−

NiSO4 disassociates into Ni2+ and SO4 2−

MgSO4 disassociates into Mg2+ and SO4 2−
Na2 SO4 disassociates into 2 Na+ and SO4 2−
With this, we can now calculate the van ’t Hoff factors for each of these. Labeling i1 for CuSO4
and so on, we have
i1 = 1 + 1 = 2
i2 = 1 + 1 = 2
i3 = 1 + 1 = 2
i4 = 2 + 1 = 3
Because Na2 SO4 has the highest van ’t Hoff factor, it will have the most depression in freezing
point. Thus, the hydrated salt with the lowest freezing point is Na2 SO4 · 10H2 O , or D .

7. In order to identify if a gas evolution reaction, we need to write out the reactions for
all the answer choices.
3
A : Al + 3 H+ −−→ Al3+ + H2 (g)
2
B : Zn + 2 H+ −−→ Zn2+ + H2 (g)
C : 2 H+ + CO3 2− −−→ + H2 O + CO2 (g)
D : no reaction, all ions are spectators
The only one of these reactions that does not cause a gas evolution reaction is D .

2
8. CaS is a precipitate in water with a relative high Ksp , so it is soluble in acid with the
weak electrolyte H2 S formed.

CaS(s) + 2 H+ (aq) −
)−
−* 2+
− Ca (aq) + H2 S(aq)
MnS and ZnS are both sulfides of transition cations, which are less soluble in water but still sol-
uble in strong acids with a similar reaction to that of CaS(s). CdS, a sulfide of the fifth period
element Cd2+ , has the smallest solubility in water here and even not soluble in hydrochloric
acid. Thus, the correct answer is Cd2+ , or D .

More specifically, the order of of hardness of the four cations from harder to softer are

Ca2+ > Mn2+ > Zn2+ > Cd2+

according to hard-soft acid-base theory (HSAB), which states higher charged and smaller sized
cations are harder Lewis acids; More electronegative, lower charged, and smaller sized anions
are harder Lewis bases. S2 – , relative 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. This is
why CdS is the only sulfide precipitate here which is not soluble even in strong acids.

9. The key fact to understand here are that transition metals produce colored compounds
and ions. By analysis of the answer choices, KMnO4 seems to be the only answer choice with
a transition metal in the compounds (MnO4 – is purple). Thus, the answer must be A .

10. AgF is soluble in water, while SrF2 is not. This means the answer is NaF, or B . For a
more detailed explanation, refer back to the solution for the USNCO Local Exam 2019 #9.

11. A beaker does not have accurate measurements, so D can be eliminated. A 10-mL volu-
metric flask or a 10-mL volumetric pipet is built to measure exactly 10 mL of solution, not 2.7
mL, so B and C can be eliminated. This leaves the 10-mL graduated cylinder , or A , which
gives the right precision.

12. To begin our analysis, phenolphthalein is pink in basic solutions getting darker as pH
increases, while colorless in acidic and neutral ones. We also note that the endpoint in a col-
orimetric titration is when the indicator changes color.

Now, we look at the answer choices. Spilling acid indicates a use of less base, which will
therefore underestimate the moles of acid. Thus, by spilling acid, we will overestimate the mo-
lar mass. In addition, the solution being a dark red indicates that the solution is overtitrated.
This color also indicates that the solution is highly basic, and more base was added than needed.
Thus, the endpoint is not accurate and the answer is B .

13. The particles in the diagram are moving quickly and in random directions, and they
are colliding with the walls of the container. They are fairly evenly spaced throughout the
container. This is characteristic of a gas , or A .

14. The strongest intermolecular forces in acetone are only dipole-dipole, while the intermolec-
ular forces in propanol include hydrogen bonding. It is well known that hydrogen bonding is
stronger than regular dipole-dipole interactions, and boiling point increases with intermolecular
force strength, the answer must be D .

15. The formula for root mean square molecular speed is the following, where M is the molar
mass. r
3RT
vrms =
M
From this we see that the order of increasing average molecular speed is also of decreasing molar
mass at the same temperature. The gases are ordered by decreasing molar mass in B .

3
16. Ideal gases are gases with the assumptions of no intermolecular forces among gas molecules
and negligible molecular size compared to the distance among them. High temperature will
increase the kinetic energy of the particles so that they will no longer be under the influence of
intermolecular forces. Low pressures will cause the particles to spread farther apart which can
neglect the size of gas molecules themselves. Thus, the only correct answer is I , or A .

17. Ionic compounds conduct electricity in the aqueous and molten states, but not in the
solid state. This is because the ions in solids are fixed in the lattice, and cannot move freely.
They also have high melting points and are often soluble in water. Thus, the only answer that
fits the conditions of the question is C .

18. Typically, a liquid with a higher vapor pressure has relative lower normal boiling point,
since normal boiling point is the temperature when the vapor pressure equals to the atmospheric
pressure (1 atm)

Lower heat of vaporization tends to lead to higher vapor pressure, as molecules more eas-
ily enter the gaseous phase. We can confirm this with the equation for equilibrium constant
KP and vapor pressure of a vaporization process as follow.

A(l) −
)−
−*
− A(g)
∆Hvap
ln KP = − +C
RT
KP = Pvapor
So,
∆Hvap
ln P = − +C
RT
Where C is a constant specific to the molecule.
∆H
If we plot ln P with 1/T for a certain liquid, a linear curve is obtained with a slope of − Rvap .
The only reasonable explanation for toluene having a higher vapor pressure at 25◦ C and higher
normal boiling point is that toluene has a lower heat of vaporization, ∆Hvap . With this in mind,
the two lines in the figure of ln P vs 1/T for toluene and water cross at a certain point with
a temperature between 25◦ C and the normal boiling point of toluene. Line for toluene has a
less native slope, which is under the line for water before the cross point, but above the line for
water after the cross point.

19. The energy the water gained in addition to the energy the aluminum block lost must
be 0.    
J ◦
Qwater = 100.0 g 4.184 ◦ 28.00 − 25.00 C
g C
   
J
QAl = m 0.900 ◦ 28.00 − 100.0 ◦ C
g C
Q1 + Q2 = 0
(100.0)(4.184)(3.00) + (m)(0.900)(−72.00) = 0
m = 19.4 g

Thus, the answer is C .

20. ∆Hf is defined as the standard enthalpy change for the reaction that makes one mole
of product from standard state elements. B makes 2 moles, so it can be eliminated. The stan-
dard state of elemental oxygen is O2 (g), so C and D can be eliminated. A is the correct answer
because 1 mol MgO(s) is created from the elements magnesium and oxygen in their standard
states at 298 K.

4
21. First we must write the reaction for the enthalpy of formation of XeF2 .

Xe(g) + F2 (g) −−→ XeF2 (g)

The enthalpy of formation can be calculated with bond dissociation enthalpy by bonds broken
minus bonds formed. We see from the reaction that one F−F bond is broken, and two Xe − F
bonds are formed. Let x be the average bond dissociation enthalpy of an Xe − F bond. Then
we have
155 − 2x = −108

Solving for x we get 132 kJ mol−1 , which is C .

22. First we must write the reaction of formation of NH3 (g).

1 3
N2 (g) + H2 (g) −−→ NH3 (g)
2 2
Now we can use the equation ∆G◦ = ∆H ◦ − T ∆S ◦ .

∆H ◦ = (1)(−46) − (1/2)(0) − (3/2)(0) = −46 kJ mol−1

∆S ◦ = (1)(193) − (1/2)(192) − (3/2)(131) = −100. J mol−1 K−1

Remember we must use either kJ or J for everything so the units will cancel. Let’s convert ∆S ◦
to kJ.
1 kJ
∆S ◦ × = −0.100 kJ mol−1 K−1
1000 J
∆G◦ = ∆H ◦ − T ∆S ◦ = −46 − (298)(−0.100) = −16 kJ mol−1

Thus, the answer is B .

23. The first fact to establish is that vaporization is a spontaneous process. We can com-
pare the Gibbs free energy to determine if the process is spontaneous. If ∆G < 0, then the
process is spontaneous. Thus, the first statement is true.

The second statement is also true in that the change in internal energy of the system ∆U
is equal to the enthalpy change ∆H plus the work done on the system −P ∆V , where P is pres-
sure and ∆V is change in volume (which is under constant pressure and temperate). Because
volume increases during the vaporization, ∆V > 0.

∆U = ∆H − P ∆V

∆H = ∆U + P ∆V > ∆U
Thus, both I + II are true, which is answer C .

Note: Please be aware that E was also commonly used in USNCO to represent the inter-
nal energy.

24. The order of entropy for 1 mol of substance, in reference to states of matter, are

gas > aqueous, liquid > solid

For answer choices B, C, and D, all the reactions indicate a decrease in entropy with a decrease
in mole of gases. Therefore, the only possible option is

NH4 + (aq) + CH3 COO− (aq) −−→ NH3 (aq) + CH3 COOH(aq)

The entropy change of this reaction can be further interpreted as follows. The reverse reaction
actually is the neutralization of NH3 and CH3 COOH, which produces hydrated cations and
anions. The forward reaction has an increase in entropy. Thus, the answer is A .

5
25. From the reaction, we see that for each mole of CCl4 formed, 3 moles of Cl2 are con-
sumed.
3 mol Cl2
0.063 M min−1 × = 0.19 M min−1
1 mol CCl4
This is D .

26. We can model the mass of 131I at time t for a nuclear decay process based on the in-
tegrated rate law for first order reactions as follows.
t
  8.02
1
m(t) = 5.00 ×
2
131
From this equation we see after each 8.02 d, half of the I will decay. Plugging in 6.01 d for
t gives 2.97 mg , or C .

27. The integrated rate law for a second-order reaction is

1 1
= kt +
[A] [A]0

We see that the graph of 1/[A] as a function of time is linear, so the answer is C .

28. According to the Arrhenius equation, rate constant k is related to both activation en-
ergy Ea and a constant specific to the reaction, C.
Ea
ln k = − +C
RT
Additionally, reaction rate is also dependent on the concentrations of reactants, thus, we can
eliminates both option A and B.
Another form of Arrhenius equation states that
   
k2 Ea 1 1
ln = −
k1 R T1 T2

Thus,
  observing the Arrhenius equation, an increase in Ea will also indicate an increase in
ln kk21 , given same increase in temperature. Thus, the reaction rate varies more with temperature ,

and the answer is D .

29. We can use a pre-equilibrium approximation (PEA) to the first step since it is a fast
reversible reaction followed by a slow step.
1k
−−*
NO + Br2 ) −− NoBr2 (fast)
k−1

We will define k−1 as the rate constant of the backward reaction of the first step.

2 k
NO + NOBr2 −
)−
−*− 2 NOBr (slow)

According to the assumption of PEA, we can say the forward reaction rate of the first step
equals to the backward reaction rate.

forward rate = k1 [NO][Br2 ]

backward rate = k−1 [NOBr2 ]

Setting these rates equal to each other, we get

k1 [NO][Br2 ] = k−1 [NOBr2 ]

6
Solving for the intermediate [NOBr2 ], we get

k1
[NOBr2 ] = × [NO][Br2 ]
k−1

Since the second step is the only reaction to produce the product, so the overall reaction rate
can be expressed by the second step only.

rateoverall = ratesecond step = k2 [NO][NOBr2 ]

Substituting [NOBr2 ] into the above equation, we get

k1 k2
rate = × [NO]2 [Br2 ]
k−1

Thus, the correct answer is B .

30. From the reaction, NOBr2 (g) is produced and then consumed, which is an intermediate ,
or A .

31. The dissolution of AgCl can be written as follows.

−−* + −
AgCl(s) )−− Ag (aq) + Cl (aq)

Let [Ag+ ] = [Cl− ] = S, where S is the molar solubility.

S 2 = Ksp
p mol
Ksp = 1.8 × 10−10 = 1.34 × 10−5
p
S=
liter
Now, we can set the molarities equal to find the mass solubility m.
m mol
mol 143.4 g
1.34 × 10−5 =
liter 1 liter

m = 1.34 × 143.4 × 10−5 = 0.00192 g = 1.92 mg

Thus, the answer is B .

32. C6 H5 COO− is the conjugate base of C6 H5 COOH. Therefore, we can use Kb = Kw

Ka to
solve this problem.
C6 H5 COO− + H2 O )−−−*
− C6 H5 COOH + OH
−

[OH− ][C6 H5 COOH]

Kb =
[C6 H5 COO− ]
Kw 10−14
Kb = = = 1.5 × 10−10
Ka 6.5 × 10−5
Let x be the amount of C6 H5 COO− that dissociates into OH− and C6 H5 COOH. We can make
the approximation that x is negligible compared to 0.20 M , and that the initial [OH− ] produced
by water is also negligible. Then we get

x2
Kb = −→ x = 5.5 × 10−6 M = [OH− ]
0.20

pH = 14 − pOH = 14 + log [OH− ] = 14 + log(5.5 × 10−6 ) = 8.74

Thus, the answer is B .

7
33. From the reaction, we use products over reactants to get
(PSO3 )1
Kp = 1
(PSO2 )1 (PO2 ) 2
0.332
Kp = 1 = 1.86
(0.562)(0.101) 2
Thus, the answer is A .

34. The reaction requires a heat input because it is endothermic. We can think about the
reaction as
−−
heat + PCl3 + Cl2 ) −*
− PCl5
According to Le Chatelier’s Principle, if we increase the temperature (add heat), equilibrium
shifts to the right, increasing the number of moles of PCl5 . Thus I is correct.

For volume, we see from P V = nRT that if volume increases, pressure decreases. In response,
the system will shift to the side with more moles of gases to reduce the pressure increase, ac-
cording to Le Chatelier’s Principle. This means equilibrium will shift towards PCl3 and Cl2 , so
II is incorrect. Thus, the answer is A .

35. The ionization of an acid in the general form of HA can be expressed as show below.
−− + −
HA )−*
−H +A
We can also determine the acidity constant Ka from this

[H+ ][A− ]
Ka =
[HA]

Upon ionization, both [H+ ] and [A− ] will be 2.3% ionized, with both concentrations equal.

[H+ ] ≈ [A− ] = 0.12 × 0.023 = 0.0028 M

Thus, the concentration of the remaining [HA] is 0.12 − 0.0028 = 0.117 M. Substituting in our
formula for Ka , we get
(0.0028)2
Ka = = 6.5 × 10−5
0.117
Thus, the answer is C .

36. In order to find the relationship between solubility and pH, first, we write down the
equation to show the dissolution equilibrium of CaF2 (s).
2+ −
CaF2 (s) −
)−
−*
− Ca (aq) + 2 F (aq)
According to mass balance equation, we can get the sum of [F – ] and [HF] is always two times
of [Ca2+ ] no matter how much F – is converted to HF.

[F− ] + [HF] = 2[Ca2+ ]

Assume S is the molar solubility of CaF2 (s), and S = [Ca2+ ], then

[F− ] + [HF] = 2S

To find the acid dissociation constant Ka , we say that

[H+ ][F− ]
Ka =
[HF]
Solving for [HF], we get
[H+ ][F− ]
[HF] =
Ka

8
Now, we can substitute this into the equation we previously got in terms of S, and we get

[H+ ][F− ]
[F− ] + = 2S
Ka

Solving for [F− ], we get

2S
[F− ] = [H+ ]
1+ Ka

We also have an additional equation in terms of Ksp , which is

Ksp = [Ca2+ ][F− ]2

Substituting the equation we got for [F− ], we get

 2
2S
Ksp = S × [H+ ]
1+ Ka

Our final goal is to solve for S, so we now get

4S 3
Ksp =  2
[H+ ]
1 + Ka

Thus, solving for S, we get s

3 Ksp (Ka + [H+ ])2
S=
4K2a
Finally, we substitute at pH’s of 3.00 and 7.00 to get
s 2
spH=3.00 3 10−3.17 + 10−3.00
= = 1.83
spH=7.00 10−3.17 + 10−7.00

Thus, the correct answer is B .

37. We need to calculate the oxidation states of the other molecules to start. For the purpose
of brevity, denote O(n) as the sum of oxidation states of a group of atoms.

O((Si4 O11 )2 ) = 2 × (4 × 4 + (−2) × 11) = −12

O((OH)2 ) = 2(−2 + 1) = −2
O(Na2 ) = 2(1) = +2
The global oxidation state must be 0, so we can set up an equation

0 = −12 − 2 + 2 + O(Fe5 )

O(Fe5 ) = +12
Now we need to allocate the distribution of oxidation states to the ions. Because Fe usually
has oxidation states that vary between +2 and +3, we need to have an integral amount of +3
(namely 2 ), and an integral amount of +2 (namely 3 ) so 3 × 2 + 2 × 3 = 12. Thus, the answer
is B .

38. Because the bromine ion is a negatively charged ion, it will travel to the anode in order to
be oxidized with Br2 produced (i.e lose electrons). The hydrogen gas, however, is going to be
evolved in the cathode . This is because hydrogen is a positively charged ion, and will travel
to the cathode to be reduced (gain electrons). Thus, the answer is A .

9
39. This is a redox reaction between KMnO4 and H2 O2 , so we need to figure out the ratio
of these two reactants to solve the stoichiometry here. Under acidic condition, the +7Mn in
KMnO4 is reduced into Mn2+ with 5 electrons gained per KMnO4 , and H2 O2 is oxidized into
O2 (g) with 2 electrons lost per H2 O2 . So the molar ratio of KMnO4 to H2 O2 is supposed to be
2 : 5 at the end point when the presence of extra MnO4 – showing a pale purple color.

We can calculate the remaining mass of the hydrogen peroxide by stoichiometry and dimensional
analysis.
0.0200 mol KMnO4 5 mol H2 O2 34.01 g H2 O2
22.50 mL × × × = 0.0383 g H2 O2
1000 mL 2 mol KMnO4 1 mol H2 O2
0.0383 g
Finding the percent solution we do 1.00 g × 100% = 3.83% , or C .

40. From the line notation, we see that nickel is the anode and silver is the cathode.
◦ ◦ ◦
Ecell = Ecat − Eano = +0.80 − (−(0.23)) = 1.03 V

This is C .

41. This is a concentration cell, which reaches equilibrium when both compartments have
the same concentration of Cu2+ . So the compartment with 1.0 M Cu2+ solution will be the
cathode (reduction), and the compartment with 0.10 M Cu2+ solution will be the anode (oxi-
dation).
1.0 M compartment − Cu2+ + 2 e− −−→ Cu2+
0.10 M compartment − Cu −−→ Cu2+ + 2 e−
Thus, the overall reaction is

Cu2+ [1.0 M] −−→ Cu2+ [0.10 M]

Thus, the electron flow will go from the electrode in the 0.10 M solution to the electrode in 1.0
M solution.
However, we still need to determine cell potential by using Nernst’s equation.

[Cu2+ ]anode
 
0.059
Ecell = Ecell ◦ − × log10
n [Cu2+ ]cathode

We know that the number of electrons (n) is 2. We additionally know that Ecell ◦ = 0 because
the given cell is a concentration cell. Substituting this additional information, we have
 
0.059 0.10
Ec = − × log10
2 1.0

0.059
Ec = − × (−1)
2
Ec = 0.0295 V ≈ 30 mV

Thus, the answer is C .

42. We know that the charge Q is equal to nF N , where n is the number of electrons transferred
per mole of analyte, F is Faraday’s constant which is the charge of 1 mole of electrons, and N
is the number of moles of analyte. We also know that Q = I × te , when I is the current and te
is the time of electrolysis. We can set these equal to each other, and solve for N .
 
C
(670 sec)(0.10 A) = (1) × 96500 × (N )
mol

N = 6.9 × 10−4 mol Ag

10
We can just multiply by the molar mass to determine the grams of Ag.
107.8682 gAg
6.9 × 10−4 mol Ag × = 0.075 g Ag
1 mol Ag
Then we can do the mass ratio and determine the percentage
0.075 g Ag
× 100 % = 7.5 % −→ D
1.00 g
.

43. The electron configuration of Al is [Ne]3s2 3p1 . For Al3+ we must remove three elec-
trons, leaving us with the same electron configuration as neon. The electron configuration of
neon is 1s2 2s2 2p6 , or A .

44. Tungsten, W, has the highest melting point of all metals. Metals tend to have higher
melting points as they get closer to W. Fe is the closest to W on the periodic table, so the
answer is C .

In general, the boiling and melting point of metals increases with increasing number of va-
lence electrons because there is an increased force of attraction between the metal cations and
the valence electrons according to the electron-sea model.

45. There is a formula relating energy and wavelength, which is below

hc
E=
λ
where h is Plank’s constant, c is the speed of light, and λ is the wavelength. We can substitute
our known values to solve for E.
(6.626 × 10−34 J × s)
 
8 m
E= × 2.998 × 10
538 × 10−9 m s

E = 3.69 × 10−19 J

Thus, the answer is A .

46. n = 3 and l = 1 refers to a 3p orbital. Writing the electron configuration for arsenic,
we see 3p6 , meaning that all three orbitals in the 3p subshell are full. Since there are 2 elec-
trons in each full orbital, the answer is C .

47. From our periodic trends, ionization energy decreases down and to the left. K is closest
to the bottom left of the periodic table, so the answer is C.

48. Method of elimination can be used for solving this question. Option A states that elec-
tronegativity increases down the group, which is not true based on the periodic trends. Simi-
larly, option C is also incorrect since the polarity of X−H bond decreases down the group as the
electronegativity of X decreases. The statement in option D about bond angle is obviously not
related to the acid strength. Thus, only option B is reasonable, and can be used to explain
the trend of acid strength. Thus, we get answer choice B .

The strength of acids can be analyzed through the stability of their conjugate bases. The
more stable the conjugate bases, the stronger the acids. Comparing the four conjugate bases,
HO− , HS− , HSe− , HTe− , we can see that size of the 16-group elements increases down the
group, so the polarizability of the anions is also increasing. Polarizability is defined as the
tendency of an atom, an ion or a molecule’s electron cloud to be distorted. The polarizability
increases with the total number of electrons in the species. Thus, larger species are more po-
larizable than smaller ones.

11
49. PF3 has covalent bonds between P and F. KF is an ionic compound. CH3 COOH is
an organic compound with only covalent bonds. MgSO4 has an ionic bond between the Mg2+
and the SO4 2− . There are covalent bonds between the S and the O in SO4 2− . Thus, the answer
is D .

50. The Lewis structure for SO2 has S in the center as the least electronegative element.
There are two double bonds. Because sulfur has two bonding groups and one lone pair, the
molecular geometry is bent, so the answer is B .

51. The major resonance of ClO3 – is shown as follow

O
Cl
O O
The single bonded oxygen carries a negative formal charge. We see from the structure that Cl
has 1 lone pair, or B .

52. Although tetrahedral molecules such as CH4 are often drawn as squares on paper, they
are not really squares. Visualizing a 3D tetrahedral molecule such as CF2 Cl2 , we see that
swapping an F with a Cl leads to the same molecule, only rotated. In contrast, visualizing a
2D square planar molecule such as XeF2 Cl2 , we see that swapping an F with a Cl leads to
a different molecule that cannot be obtained by simply rotating the initial molecule, which
are marked as cis and trans isomers. Therefore a pair of geometric isomers is consistent
only with a square planar geometry , which is B .

53. O2 is a typical paramagnetic molecule with unpaired electrons, which can be explained
by the molecular orbital diagram of the O2 as shown below. With 6 bonding electrons and 2
unpaired anti-bonding electrons in the valence shell, the bond order in O2 is calculated to be 2
(equivalent to a double bond) based on the equation for bond order as shown below.
1
Bond order = (number of bonding e− − number of antibonding e− )
2
With one electron removed from O2 , O2 + has one less electron in the anti-bonding orbital, and
therefore, the bond order in O2 + is 2.5. This bond is stronger than the double bond in O2 which
explains the shorter bond. Because bond order increases by 0.5 for each antibonding electron
that is removed, we can reason that A is the correct answer. Below is the molecular orbital
diagram for O2 .

54. When we draw the Lewis structure of the guanidinium ion, we find the carbon makes three
single bonds with each nitrogen and carries a positive formal charge. Each nitrogen makes two
N−H bonds, one N−C single bond and a lone pair. It seemed like the nitrogen atoms need to
be sp3 hybridized with a trigonal pyramidal geometry according the VSEPR model. But if we
draw all of the resonances structures, we find that there are three more resonances in which

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there are one C−N and two C−N with the double bonded nitrogen carrying the positive formal
charge and no lone pair. Then we can conclude each nitrogen needs to be sp2 hybridized with
a trigonal planer structure in order to make the delocalized system among all three nitrogens
and the central carbon atom, which is D .

55. From the name propyne, we know the compound is an alkyne and so must have a triple
bond between carbons. Drawing the molecule, we count one triple bond and no double bonds.
There are 2 π bonds for each triple bond, so the answer is C .

56. For this problem, we must draw out all isomers.

H Cl
C C
Cl H
H H
C C
Cl Cl
H Cl Cl H
C C C C
H Cl Cl H
Note that the second two ”isomers” are actually identical to each other. We can obtain one by
flipping the other in space. This leaves us with 3 isomers, which is C .

57. A molecule with a chiral carbon is called chiral, which can’t be superimposed with its
mirror image, similar to our left hand and right hand. And the carbon atom with four different
groups connected is called a chiral carbon. Thus, when HC is replaced by Br in 1-butene, the
carbon with HC originally connected changes into a chiral carbon with four different groups
connected, which are −H, −Br, −CH3 , and −HC−CH2 . So the correct answer is C .

58. Halogens react quickly with alkenes such as hexene, which is done by adding two bromines
to each carbon in the double bond known as addition reaction. This decolorizes bromine as the
bromine becomes attached to the organic compound rather than retaining its own form with
a reddish brown to yellow color depending on its concentration. However, cyclohexane does
not react with bromine at room temperature, since there is no double bond present to have a
similar addition. Thus the answer is A .

59. The dehydration of alcohol under the the catalysis of acid yields different alkenes if there
are different types β hydrogens in the alcohol. In organic chemistry, the hydrogen atoms con-
nected to the β carbon(s) are commonly called β hydrogens, and β carbons are those adjacent
to the α carbon with functional group (−OH in alcohols and −Br in alkyl bromides) connected.
Similarly, alkyl halides react with strong bases to yield different alkenes through the elimination
of hydrogen halides molecules. By analyzing the types of β hydrogens in each starting material
in option A, B, C, and D, we can find, both A and C yields two alkenes with different structures,
D yields three different alkenes, only B , a tertiary alcohol with three equivalent R groups,
yields only one single type of alkene.

60. Photosynthesis is endothermic because it requires energy input from the sun. It forms sugars
because it is the reverse reaction of cellular respiration, which breaks down sugars. Thus, the
answer is B .

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