CHM 3609 Inorganic Chemistry: Homework 6
Practice Questions:
100 points total
Note: Answers should be neatly written in separate papers with question number clearly
indicated.
1. On the basis of molecular orbitals, predict the shortest bond, and provide a brief explanation.
a. Li2+ Li2
b. F2+ F2
c. He2+ HHe+ H2+
a. Li2 has a bond order of 1.0 (two electrons in a σ bonding orbital; see
Figures 5.7 and 5.1 of Miessler 5th ed.). Li2+ has a bond order of only 0.5 (one electron in a
σ bonding orbital). Therefore, Li2 has the shorter bond.
b. F2 has a bond order of 1.0 (see Figure 5.7). F2+ has one less antibonding (π*)
electron and a higher bond order, 1.5. F2+ would be expected to have the shorter bond.
c. Expected bond orders (see Figure 5.1):
Bonding electrons Antibonding electrons Bond order
He2 + 2 1 ½*(2 – 1) = 0.5
HHe + 2 0 ½*(2 – 0) = 1
H2 + 1 0 ½*(2 – 1) = 0.5
+ + +
Both He2 and H2 have bond orders of 0.5. HHe would therefore be expected to have the
shortest bond because it has a bond order of 1.
2. On the basis of molecular orbitals, predict the weakest bond, and provide a brief explanation.
a. P2 S2 Cl2
b. S2+ S2 S2‒
a. These diatomic molecules should have similar bond orders to the analogous
diatomics from the row directly above them in the periodic table:
P2 bond order = 3 (like N2)
S2 bond order = 2 (like O2)
Cl2 bond order = 1 (like F2) Cl2 has the weakest bond.
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b. The bond orders match those of the analogous oxygen species (see Miessler Section
5.2.3):
S 2+ bond order = 2.5
S2 bond order = 2
S 2– bond order = 1.5 S2– has the weakest bond.
3. Although the peroxide ion, O22‒, and the acetylide ion, C22‒, have long been known, the
diazenide ion N22‒ has only been prepared much more recently. By comparison with the other
diatomic species, predict the bond order, bond distance, and number of unpaired electrons for
N22‒. (See G. Auffermann, Y. Prots, R. Kniep, Angew. Chem., Int. Ed ., 2001 , 40 , 547.)
The MOs are similar as in Figure 5.5 and 5.7 in Miessler Textbook.
Bond Order Bond Distance (pm) Unpaired Electrons
C22– 3 119 0
N22– 2 122.4 2
O22– 1 149 (very long) 0
O2 2 120.7 2
The bond distance in N22– is very close to the expected bond distance for a diatomic with 12
valence electrons, as shown in Figure 5.8.
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4. a. Prepare a molecular orbital energy-level diagram for NO, showing clearly how the atomic
orbitals interact to form MOs.
b. How does your diagram illustrate the difference in electronegativity between N and O?
c. Predict the bond order and the number of unpaired electrons.
d. NO+ and NO‒ are also known. Compare the bond orders of these ions with the bond order
of NO. Which of the three would you predict to have the shortest bond? Why?
a. The energy level diagram for NO is on
the right. The odd electron is in a π2p* s 2p *
orbital.
p 2p *
b. O is more electronegative than N, so 2p
its orbitals are slightly lower in energy.
The bonding orbitals are slightly more s2p 2p
concentrated on O. p2p
c. The bond order is 2.5, with one unpaired s2s*
electron. 2s
2s
s 2s
d. NO+ Bond order = 3
N NO O
shortest bond (106 pm)
NO Bond order = 2.5
intermediate (115 pm)
NO– Bond order = 2
longest bond (127 pm), two electrons in antibonding orbitals.
5. a. Prepare a molecular orbital energy-level diagram for the cyanide ion. Use sketches to show
clearly how the atomic orbitals interact to form MOs.
b. What is the bond order for cyanide, and how many unpaired electrons does cyanide have?
c. Which molecular orbital of CN‒ would you predict to interact most strongly with a hydrogen
1s orbital to form an H‒C bond in the reaction CN‒ + H+ → HCN? Explain.
a. The CN– energy level diagram is similar to that of NO (Problem 4) without the
antibonding π* electron.
b. The bond order is three, with no unpaired electrons.
c. The HOMO is the 2p orbital, which can interact
with the 1s of the H+, as in the diagram at right.
The bonding orbital has an energy near that of the
π orbitals; the antibonding orbital becomes the
highest energy orbital.
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6. Although KrF+ and XeF+ have been studied, KrBr+ has not yet been prepared. For KrBr+:
a. Propose a molecular orbital diagram, showing the interactions of the valence shell s and p
orbitals to form molecular orbitals.
b. Toward which atom would the HOMO be polarized? Why?
c. Predict the bond order.
d. Which is more electronegative, Kr or Br? Explain your reasoning.
s*
a. The KrBr+ energy level diagram is at the right.
HOMO
p*
b. The HOMO is polarized toward Br, since its 4p
4p
energy is closer to that of the Br 4p orbital. p
s
c. Bond order = 1
d. Kr is more electronegative. Its greater s*
4s 4s
nuclear charge exerts a stronger pull on
the shared electrons. s
Kr KrBr+ Br
7. Prepare a molecular orbital energy level diagram for SH‒, including sketches of the orbital
shapes and the number of electrons in each of the orbitals.
The energy level diagram for SH– is shown below. A bond order of 1 is predicted.
The S orbital energies are –22.7 eV (3s) and –11.6 eV (3p); the 1s of H has an energy of –
13.6 eV. Because of the difference in their atomic orbital energies, the 1s orbital of
hydrogen and the 3s orbital of sulfur interact only weakly; this is shown in the diagram
by a slight stabilization of the lowest energy molecular orbital with respect to the 3s
orbital of sulfur. This lowest energy orbital is essentially nonbonding. These orbitals are
similar in appearance to those of HF, with more balanced contribution of the hydrogen
1s and sulfur valence orbitals since the valence orbitals of sulfur are closer to the energy
of the hydrogen 1s orbital than the valence orbitals of fluorine.
s*
3p
1s
3s
s
H SH– S