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Chemistry 121
Second midterm exam
October 22, 2009
Rules:
constant or unit conversion factor that is not provided, you may ask the proctor. This exam
must represent your own work!
3. Sign your exam with the honor pledge below:
Scores:
1 25
2 20
3 25
4 20
5 20
6 20
7 20
Total points 150
Page 2 of 7
1) (20 pts) Photoelectron spectroscopy of sodium atoms excited by X‐rays with wavelength 9.890 x
10‐10 m shows four peaks in which the electrons have speeds of 7.992 x 106 m/s, 2.046 x 107
m/s, 2.074 x 107 m/s, and 2.099 x 107 m/s. Given 1 J = 1 kg m2 s‐2, and KE = ½ mv2
a) Using your understanding of the quantum structure of the atom explain why there are four
peaks.
Na has 11 electrons total. Two are in the n=1 shell, 8 are in the n=2 shell and 1 is in the n=3
shell (the electron configuration is 1s22s22p63s1). However, the n=2 shell has two subshells
with l=0 and 1 (s and p orbitals) and therefore there are actually four distinct energy levels
that electrons are occupying.
b) Two of the peaks have very similar energies while the other two are quite different. Explain
why two are so similar but not identical. Include in your explanation the factors which are
similar and the factors which differ between these two types of electrons.
The electrons in the 2s and 2p subshells will have similar energies that are distinct from the electrons
in the 1s and 3s subshells. With increasing principle quantum number the electrons are on average
located farther from the nucleus, penetrate less and therefore experience less coulombic attraction.
Also, the effective nuclear charge decreases as the principle quantum number increases so the 3s
electron feels a much lower effective nuclear charge than the 2s, 2p and 1s electrons. So we would
expect the IEs of electrons in orbitals to be 1s>2s>2p>3d.
The difference in energies of the 2s and 2p electrons arises from differences in orbital penetration
and shielding. The 2s orbital has an average r that is farther from the nucleus than the 2p orbital, but
in the 2s orbital there is a region of electron density located quite close to the nucleus – it penetrates
closer to the core. Therefore electrons in the 2s orbital will experience a higher effective nuclear
charge, whereas the 2p orbitals are more effectively shielded from the nuclear charge.
c) Calculate the ionization energy in kJ/mol of the electrons which have the largest ionization
energy.
The electron with the lowest KE will have the highest IE since Ehv = IE + KE, these are the 1s
electrons with a velocity = 7.992x106 m/s.
6.626 10 2.998 10 1
6.022 10
9.890 10 1000
1.2096 10 /
The KE of the photoelectrons is
9.109 10 7.992 10 6.022 10 1.7512 10 /
So the IE of sodium 1s electrons= 1.2096x105 kJ/mol – 1.7512x104 kJ/mol = 1.0345x105
kJ/mol
Page 3 of 7
2) (20 pts) Indicate whether energy is absorbed or emitted when the following electronic
transitions occur in a hydrogen atom and briefly explain your reasoning.
a) An electron moves from a n=4 to the n=2 state
Energy is released. An electron located in the n=2 state is, on average, closer to the nucleus
than an electron in the n=4 state. The closer an electron is to the nucleus, the lower the
electron energy so the electron is moving from a high energy state to a low energy state and
must give up energy
b) An electron moves from the 3s to the 3p state
No energy is absorbed or released. In the hydrogen atom energy is only dictated by the
principle quantum number (remember that En=‐hR(1/n2)) and so the energy of an electron in the
3s subshell is exactly the same as the energy of an electron in a 3p subshell.
c) An electron moves from an orbital with average r = 2.12 Å to one with an r = 8.46 Å
Energy is absorbed. As stated in part a) the closer an electron is to the nucleus the lower its
energy. So in this transition the electron is going from a lower energy state to a higher
energy state, and therefore energy must be added.
d) An electron is added to a H+ ion and ends up in a 3d orbital
Energy is released. Electrons always experience some coulombic attraction towards the
nucleus, no matter what orbital they are in. An electron being added to an H+ ion, will go from
experiencing virtually zero coulombic attraction, to experiencing significant coulombic attraction
and therefore its energy will be decreased and energy will be given off.
Page 4 of 7
3) (25 pts) Mixing SbCl3 and GaCl3 in a 1:1 molar ratio gives a solid ionic compound of empirical
formula GaSbCl6. A controversy arises over whether this compound in [SbCl2]+ [GaCl4]‐ or
[GaCl2]+ [SbCl4]‐
a) For each ion, draw appropriate Lewis dot structures which minimize the formal charge on all
atoms. State the electron domain geometry, then sketch and name the molecular geometry
[SbCl2]+ A=18 electrons, and three possible Lewis structures are shown below (the first is most
significant. In all cases there are three electron domains around the antimony, and
therefore the
molecular
geometry would
be bent.
[GaCl4]‐ A=32 electrons, and one possible Lewis
structure shown below. There are four electron domains
around the gallium, and therefore the molecular geometry
would be tetrahedral.
[GaCl2]+ A=16 electrons, and there are several possible resonance structures, shown below, in all
cases there are two electron domains around gallium, and therefore the molecular geometry is linear.
[SbCl4]‐ A=34 electrons, and there are 5 electron
domains around the central atom, therefore the
molecular geometry is see‐saw
b) Experimental evidence suggests that the cation in the compound has a dipole moment.
Based on this fact, which compound [SbCl2]+ [GaCl4]‐ or [GaCl2]+ [SbCl4]‐ is more likely to be
correct?
The cation in [SbCl2]+ [GaCl4]‐ has a bent geometry, which would result in a net dipole
moment, whereas in [GaCl2]+ [SbCl4]‐ the cation has a linear geometry, with no dipole
moment. Therefore [SbCl2]+ [GaCl4]‐ must be the correct structure.
c) For the molecular ion [GaCl4]‐, state whether the ion has an inversion center, horizontal or
vertical mirror planes, and what axes of rotation.
The anion is tetrahedral, and has no inversion center or horizontal mirror planes, but does
have 4 C3 rotation axes, 3 C2 rotation axes, and a vertical mirror plane (plane of the paper)
Page 5 of 7
4) (20 pts) Methyl isocyanate, CH3NCO (the N is bonded to two C atoms), was involved in the
disaster in Bhopal, India in 1984 where it is estimated to have killed over 25,000 people.
a) Draw its Lewis dot resonance structures and indicate the formal charges on each atom.
b) Predict which resonance structure you have drawn will contribute the most to the actual
resonance hybrid structure and explain your choice.
The structure on the left will contribute the most to the actual resonance hybrid structure.
The formal charges on all atoms are zero, which is the lowest energy configuration.
5) (20 pts) A student was asked to explain experimental observations which demonstrate that the
energies of electrons in atoms are quantized. Assess the accuracy of the following response:
All atoms emit only radiation with frequencies predicted by the Rydberg equation. By
Einstein’s equation, each frequency corresponds to a specific energy. Therefore, each
frequency is a specific energy of an electron in an atom, and this energy is equal to the
kinetic energy the electron has when it is ejected by a photon. Since there are many
electrons, there are many different frequencies, each predicted by the Rydberg equation, so
only certain energies are possible.
The first sentence is incorrect, only hydrogen atoms emit radiation with frequencies predicted by the
Rydberg equation. Other atoms do emit radiation, each with a characteristic set of frequencies, but
the Rydberg equation does not predict the frequencies.
The second sentence is close. More specifically, each frequency corresponds to a specific photon
energy, as given by the equation E=hν, and this is the energy emitted by the atom.
The third sentence is incorrect, each frequency corresponds to a change in energy of an electron in
an atom, and this energy is equal to the difference between the two quantum states. The kinetic
energy an electron has when emitted by a photon is equal to the energy of the incoming photon
minus the ionization energy.
The fourth sentence, not surprisingly, is also incorrect. Regardless of the number of electrons in an
atom, many frequencies of light are emitted because the atom’s electron(s) can occupy many
different quantum levels, and each transition between quantum levels causes energy to be emitted
or absorbed. Again, only the H atom transitions are predicted by the Rydberg equation. But the fact
that only certain frequencies are seen does indicate that only certain electron transitions are
possible, and that suggests that electron energy is quantized, that electrons only have certain
energies within the atom.
Page 6 of 7
6) (20 pts) A novice chemist prepares a compound having the formula NF5. You, a wiser and more
experienced chemist believe that this is really the compound [NF4]+[F‐].
a) Explain your reasoning using your understanding of Lewis structures and the octet rule.
Nitrogen is in the second row of the periodic table and therefore cannot have an expanded
octet. So NF5 is a molecule impossible to form.
b) The novice chemist counters your argument by pointing out the existence of PF5. How can
you defend your argument?
PF5 can exist – P is in the third row of the periodic table and therefore can have an expanded
valence. But just because P and N are in the same group of the periodic table doesn’t mean
that their chemistry is exactly the same, N cannot have an expanded octet.
c) Use your knowledge of the differences between ionic and molecular compounds to predict
the properties of [NF4]+[F‐] and the hypothetical NF5 compound.
NF5 is a covalent molecule, and therefore should have relatively low melting and boiling points
and when dissolved into solution, it is a non‐electrolyte. [NF4]+[F‐] is an ionic species and
therefore should be solid at room temperature with high melting and boiling points and is an
electrolyte when dissolved in solution so should conduct electricity.
Page 7 of 7
7) (20 pts)The following table shows the ionization energies (IE) of the first 20 elements as
measured by photoelectron spectroscopy:
Element Ionization Energy (MJ/mol)
H 1.31
He 2.37
Li 6.26 0.52
Be 11.5 0.90
B 19.3 1.36 0.80
C 28.6 1.72 1.09
N 39.6 2.45 1.40
O 52.6 3.12 1.31
F 67.2 3.88 1.68
Ne 84.0 4.68 2.08
Na 104 6.84 3.67 0.50
Mg 126 9.07 5.31 0.74
Al 151 12.1 7.79 1.09 0.58
Si 178 15.1 10.3 1.46 0.79
P 208 18.7 13.5 1.95 1.01
S 239 22.7 16.5 2.05 1.00
Cl 273 26.8 20.2 2.44 1.25
Ar 309 31.5 24.1 2.82 1.52
K 347 37.1 29.1 3.93 2.38 0.42
Ca 390 42.7 34.0 4.65 2.9 0.59
a. Use these data to show that only 6 electrons can be placed in the 3p orbital.
Going from Mg to Al results in five ionization energies indicating 5 types of electrons. As additional
electrons are added as we go from Al to Si, P, S, Cl and Ar there are only 5 ionization energies, indicating
that 6 electrons can be placed into the 3p orbital. However for K, there are 6 ionization energies,
suggesting that the additional electron must go into a different orbital with different electron energies,
and therefore the 3p orbitals can only hold 6 electrons.
b. Use these data to show that the 3s orbital is filled before the 3p orbital.
The third row of the periodic table goes from Na to Ar. Na has 4 ionization energies, indicating 4 types of
electrons. Mg also has 4 ionization energies and 4 types of electrons. Al, however, has 5 types of
electrons and 5 distinct ionization energies are shown by the remainder of the elements in that row. So
we have a group of 2 and a group of 6. There is only one 3s orbital and it can only hold two electrons.
Therefore the pattern on 2+6 filling suggests that the 3s orbital fills first, and that must mean that it is
lower in energy.
c. The data show that the first IE of N is greater than that of O and the first IE of P is
greater than that of S. Explain in each case why this is true. Using this explanation and
the data, predict the relative electron affinities of N and O and state the basis of your
prediction. Using your prediction, further predict the relative electronegativities of N
and O.
The first IEs of O and S are greater than N and P because in N and P the 2p and 3p orbitals are all ½ filled.
This minimizes electron/electron repulsions and this effect outweighs the greater core charge felt by the
valence electrons in O and S. The electron affinity of O will be larger in magnitude (more negative) than N
because the additional electron added to N would have to pair and the core charge of N is smaller than
that of O and so this is energetically unfavorable. The electronegativity of O will be larger than N, as O has
a higher core charge (and is slightly smaller)