Problem Set 2*

CHEM 103, Section J01, Fall 2017

Part A Silberberg, Chapters 7 and 8

1 Draw the boundary surface of these hydrogen atomic orbitals: 3dxy, 3dx2–y2, 2pz, 1s. Label the
axes drawn. For each orbital, determine the quantum numbers n and l, and locate the nodes
(where the wavefunction vanishes to zero). Which of these orbitals are degenerate (have the
same energy) in the hydrogen atom?

3dxy n = 3, l = 2 There are two nodes: the xz plane and the yz plane

3dx2-y2 n = 3, l = 2 There are two nodes: each are rotated 45° from the xz/yz planes

2pz n = 2, l = 1 There is one node: the xy plane

*
Adapted in part from problem sets by Dr. Yoram Apelblat and Dr. Arthur Mar. ã S. Styler, Department of
Chemistry, University of Alberta, 2017.
1s n = 1, l = 0 There are no nodes.

The 3dxy, and the 3dx2-y2 atomic orbitals are degenerate in the hydrogen atom. Note: these
atomic orbitals would also be degenerate with the 3s and 3p orbitals, since the splitting of s–p–
d–f atomic orbital energies within a given energy level (n) occurs only for multi-electron
atoms!

2 Short answers:

(a) The quantum number n describes the size and energy of an orbital and l describes its shape.
(b) When n = 3, the possible values of l are 0, 1, 2.
(c) What type of orbital corresponds to l = 3? f
(d) For a 4d orbital, the value of n is 4, the value of l is 2, and a possible value of ml is -1 (or -2,
0, 1, 2).

3 Review of electron configuration:

a) Complete the following table:

b) Which of these species has a noble-gas-type configuration?

Cl– and P3– have noble-gas-type configurations.

4 Define shielding, penetration, and effective nuclear charge; describe how these concepts are
related. Use these concepts to explain why a 2p orbital lies higher in energy than a 2s orbital
in a many-electron atom.

Shielding: this refers to the effect that other electrons, especially core (inner shell) electrons,
have on reducing the nuclear charge that’s actually felt by an outer-shell electron
Penetration: an electron penetrates if it is close to the nucleus part of the time (e.g. the 2s orbital
whose radial probability distribution is depicted in the textbook)—penetration
counteracts the shielding of inner electrons such that the electron experiences a
greater-than-expected effective nuclear charge and is thereby stabilized

Effective nuclear charge (Zeff): the net positive charge that acts on a particular electron in an
atom—its value is the nuclear charge, reduced to the extent
that other electrons shield that electron from the nucleus

Although the electron density is (on average) closer to the nucleus in the 2p orbital than in the
2s orbital, the 2s orbital lies lower in energy than a 2p orbital. This is because the electrons in
the 2s orbital penetrate closer to the nucleus, as shown in the radial probability distribution
shown in the textbook, and thus experience less shielding and have a larger Zeff. As a result,
the 2s orbital is lower in energy. At the same time, the 2s electrons shield the 2p orbital from
the nuclear charge, which reduces its Zeff and raises its energy.

5 The superheavy element 114 (now called flerovium, Fl) should most closely resemble the
element Pb.

a) Write the electron configuration for Pb, and propose a plausible electron configuration for
Fl. Write a full set of quantum numbers for the outermost electron in an atom of Fl.

Pb: [Xe] 6s2 4f14 5d10 6p2

Fl: [Rn] 7s2 5f14 6d10 7p2

The outermost electron of Fl would be in a 7p orbital. The six possible full sets of quantum
numbers are: n = 7, l = 1, ml = {-1, 0, or 1}, ms = {+1/2 or -1/2}. Note that you must choose
ONE value for ml and ONE value for ms (they are all equally valid).

b) What are the group and period numbers of Fl? Is it a metal or nonmetal? Is it a main-group
or a transition element?

Fl is in Group 14

Fl is in Period 7

It is a metal (most likely).

It is a main-group element.

c) How many unpaired electrons are present, and is Fl paramagnetic or diamagnetic?

Fl has two unpaired electrons (remember Hund’s rule!) and is paramagnetic.

 d) Like Pb, the element Fl probably forms a 2+ cation. Is this ion diamagnetic or paramagnetic,
and how many unpaired electrons are present?

The Fl2+ cation should have the electron configuration: [Rn] 7s2 5f14 6d10. It should be
diamagnetic, as there are no unpaired electrons.

e) Would you expect Fl to be bigger or smaller than Pb? Would you expect its IE2 to be higher
or lower than that of Pb?

We would expect Fl to be larger than Pb, because it is lower in the periodic table. We would
expect its second ionization energy (and its first, for that matter!) to be lower than that of Pb,
because it’s larger—its outer electrons are more shielded (by another shell of core electrons),
and thus should be easier to remove.

f) Why can’t Fl achieve a noble-gas-type configuration?

Fl can’t achieve a noble-gas-type configuration because this would require it to lose 28

electrons, which would be highly energetically unfavourable.

6 The following species are isoelectronic with the noble gas krypton. Arrange them in order
of increasing radius, and comment on the principles involved in doing so: Rb+, Y3+, Br–, Sr2+, Se2–.
7 Rationalize the order of the first ionization energy values of cadmium, indium, tin and
antimony based on their electronic configurations.
Part B Stoichiometry Review
1 Cortisol (M = 362.47 g/mol), one of the major steroid hormones, is a key factor in the
synthesis of protein. Its profound effect on the reduction of inflammation explains its use
in the treatment of rheumatoid arthritis. Cortisol is 69.6% C, 8.34% H, and 22.1% O by mass.
What is its molecular formula? (Silberberg 3.47)

2 Element X forms the chloride XCl4, which contains 75.0% Cl by mass. Identify element X.
3 Elemental sulfur occurs in octatomic molecules, S8. What mass of fluorine gas is needed to
react completely with 17.8 g of sulfur to form sulfur hexafluoride? (Silberberg 3.73)

4 para-Cresol is used as a disinfectant and in the manufacture of herbicides. A 0.4039 g

sample of this carbon-hydrogen-oxygen compounds yields 1.1518 g CO2 and 0.2694 g H2O in
combustion analysis. Its molecular mass is 108.1 u. For p-cresol, determine a) its mass
percent composition; b) its empirical formula; c) its molecular formula.
5 A 0.732 g mixture of methane, CH4, and ethane, C2H6, is burned, yielding 2.064 g CO2. What
is the percent composition of this mixture, a) by mass; b) on a mole basis?

6 How many grams of solid silver carbonate form when 35.0 mL of 0.160M magnesium
carbonate reacts with 58.0 mL of 0.065M silver (I) nitrate?
7 Sodium borohydride (NaBH4) is used industrially in many organic syntheses. One way to
prepare it is by reacting sodium hydride with gaseous diborane (B2H6). Assuming an 88.5%
yield, how many grams of NaBH4 can be prepared by reacting 7.98g of sodium hydride and
8.16g of diborane? (Silberberg 3.94)
8 A compound contains only C, H and N. Combustion of 35.0 mg of the compound produces
33.5 mg CO2 and 41.1 mg H2O. What is the empirical formula of the compound?