Questions

1. What does it mean when two molecules are said to be isoelectronic? What can you say
about the bonding in molecules that are isoelectronic?

Molecules are isoelectronic if they have the same number of electrons. Typically,
isoelectronic molecules have the same number of bonds (although formal charges may be
different.)

2. Decide whether each of the following pairs of molecules is isoelectronic.

[a] CO and CN- [b] CO and C22- [c] CO and NO+

[d] N2 and O22- [e] N2 and CN- [f] CO2 and SO2
[g] CO2 and FCN [h] CO2 and NOF [i] CO2 and OCN-
[j] CO2 and OF2 [k] CO2 and NO2- [l] CO2 and NO2+
[m] NCN2- and OCN- [n] CH4 and SF4 [o] CH4 and BH4-
[p] BF3 and NF3 [q] NO3- and CO32- [r] CO32- and FNO2

[a] yes, [b] yes, [c] yes, [d] no, [e] yes, [f] no, [g] yes, [h] no, [i] yes, [j] no, [k] no
[l] yes,[m] yes, [n] no, [o] yes, [p] no, [q] yes, [r] yes

3. What is formal charge?

The charge an atom in a molecule would have if the bonding electrons are assumed to be
equally shared.

4. What is the formal charge of each of the following?

[a] A fluorine atom surrounded by one unshared and three shared electron pairs
[b] A fluorine atom surrounded by two unshared and two shared electron pairs
[c] A fluorine atom surrounded by three unshared and one shared electron pairs

[d] An oxygen atom surrounded by one unshared and three shared electron pairs
[e] An oxygen atom surrounded by two unshared and two shared electron pairs
[f] An oxygen atom surrounded by three unshared and one shared electron pairs

[g] A nitrogen atom surrounded by one unshared and three shared electron pairs
[h] A nitrogen atom surrounded by two unshared and two shared electron pairs
[i] A nitrogen atom surrounded by three unshared and one shared electron pairs
[a] 2+, [b] 1+, [c] 0, [d] 1+, [e] 0, [f] 1-, [g] 0, [h] 1-, [i] 2-

5. What is the formal charge one each of the following atoms?

[a] S in SF4 [d] P in PF5

[b] S in SF6 [e] Xe in XeF2
[c] P in PF3 [f] Xe in XeF4
6. Without referring back to the text, describe the shape of each of the following
molecules and state the orbital hybridization of the central atom.

[a] BF3 [e] BrCl5 [I] XeF2

[b] NF3 [f] PF5 [j] XeF4
[c] OF2 [g] SF4 [k] NO2-
[d] BrCl3 [h] SF6 [l] ClO2-

7. What is the difference between a sigma bond and a pi bond?

8. Nitric oxide (NO) readily loses an electron to form the nitrosonium (NO+) ion. What is
the bond order in the nitrosonium ion? Draw a structure for this ion and calculate the
formal charges on both atoms.

9. In the FNO2 molecule, the nitrogen atom is the central atom to which the others are
attached. Draw all possible resonance structures for this molecule, and state the formal
charge and hybridization of each atom in each structure. Suggest a likely shape for the
molecule.

Three structures can be drawn. The left and right structures are equivalent; however the
center structure has undesirable formal charges. The nitrogen atom is connected to three
others and is therefore sp2-hybridized; the predicted shape is trigonal planar

10. The azide ion has the formula N3-. Draw all possible resonance structures for the
azide ion, and state the formal charge and orbital hybridization of each atom in each
structure. Suggest a likely shape for the molecule.

11. The carbonate ion has the formula CO32-. Draw all possible resonance structures for
this polyatomic ion and state the formal charge of each atom in each structure. What is
the hybridization of the carbon atom in each structure?

Three structures can be drawn. Each carbon atom is connected to three others and is
therefore sp2-hybridized.
12. Dinitrogen oxide, N2O, is also known as nitrous oxide. In this molecule the atoms are
connected in the order N-N-O. Draw all possible resonance structures for the nitrous
oxide molecule and indicate the formal charge and orbital hybridization of each atom in
each structure. Are all of the structures equally good? Suggest a likely shape for the
molecule.

13. The molecule NOF is known as nitrosyl fluoride. Draw all possible resonance
structures for the nitrosyl fluoride molecule, and indicate the formal charge on each atom
in each structure. Can any structures be discounted on the basis of formal charge? If so,
which ones?

Two structures can be drawn. The rightmost structure is less desirable because it has a
formal charge on every atom, has adjacent formal charges, and places a positive formal
charge on an electronegative element (fluorine).

14 Carbonyl chloride (COCl2), also known as phosgene, was once used as a chemical
warfare agent. In this molecule the carbon atom is the central atom to which the other
three are attached. Draw all possible resonance structures for this molecule and indicate
the formal charge on each atom in each structure. Can any structures be discounted based
upon formal charge arguments? If so, which ones?

Three structures can be drawn; the first structure is the best since it lacks formal
charges.

15. The oxalate ion has the formula C2O42-. The atoms in the oxalate ion are connected in
the order O2C-CO2. Draw all possible resonance structures for the oxalate ion, and
indicate the formal charge of each atom in each structure.
16. Carbon suboxide has the chemical formula C3O2. The atoms in carbon suboxide are
connected in the order O-C-C-C-O. Draw all possible structures for carbon suboxide, and
indicate the formal charge and hybridization of each atom in each structure.

17. In the N2O5 molecule the atoms are bonded in the order O2N-O-NO2; it can be viewed
as two NO2 molecules joined through an N-O-N bond. Draw all possible resonance
structures for this molecule and indicate the formal charge of each atom in each structure.
Can any structures be discounted on the basis of formal charge? If so, which ones?

18. The OCl- ion is known as the hypochlorite ion. Draw structures for this ion in which
the atoms are connected by (a) a single bond, (b) a double bond, and (c) a triple bond.
Indicate the formal charge on each atom in each structure. Do any of the structures
violate the octet rule? If so, which ones? Which do you think is the best structure?

Oxygen is restricted to having eight electrons, however chlorine can have more. The
third structure is definitely worse, because it places a positive charge on oxygen and has
a formal charge on every atom. Between the first two, the first likely has an advantage
because oxygen is more electronegative then chlorine.
19. The ClO2- ion is known as the chlorite ion. In the chlorite ion, the atoms are bonded
in the order O-Cl-O. Draw structures for the chlorite ion that contain (a) two single
bonds, (b) a single bond and a double bond, and (c) two double bonds. Indicate the
formal charge on each atom in each structure. Which structures violate the octet rule?
Which structure is the best?

The first structure is definitely the worst, because it places a formal charge on every
atom. Between the second and third, the second likely has an advantage because oxygen
is more electronegative then chlorine.

20. The peroxide and superoxide ions have the formulas O22- and O2-. Construct
molecular orbital energy-level diagrams for these two molecules, predict their bond
order, and decide whether they should be paramagnetic or diamagnetic.

21. The dicarbide ion has the formula C22-. Construct a molecular orbital energy-level
diagram for the carbide ion, predict the bond order of the molecule, and decide whether it
would be paramagnetic or diamagnetic.

22. Explain, using a molecular orbital energy level diagram, why F22- would not be
predicted to exist.

23. Do you think the He22+ ion could exist? Why or why not? Would this ion be
paramagnetic or diamagnetic?

24. Suppose the atoms in the FCN molecule were bonded in the order C-F-N rather than
F-C-N. Draw all possible resonance structures for the CFN molecule and indicate the
formal charge on each atom in each structure. Do you think that this molecule would be
as stable as the FCN molecule? Why or why not?

The placement of F in the center of the molecule is very bad, as it forces fluorine to have
more than one bond, giving it a positive formal charge. No structure can be drawn
without formal charges, and without placing fluorine with a positive charge.
25. The hyponitrite ion has the formula N2O22-. Draw all possible resonance structures for
this molecule in which the atoms are bonded in the order N-O-O-N and in which the
atoms are bonded in the order O-N-N-O. Indicate the formal charge on each atom in each
structure. Based upon formal charge arguments, which arrangement to you think is the
most stable for this molecule?

Structures in which the atoms are bonded in the order ONNO have two formal charges,
none of them positive. Structures in which the atoms are bonded in the order NOON have
more formal charges, and furthermore place a positive charge on an electronegative
element. This arrangement is not as stable.

26. Both the cyanogen and isocyanogen molecules have the formula C2N2. In the
cyanogen molecule the atoms are bonded in the order N-C-C-N. In the isocyanogen
molecule, the atoms are bonded in the order N-C-N-C. Draw all possible resonance
structures for these two molecules, and determine the formal charge on each atom in each
structure. Based upon formal charge arguments, which arrangement to you think is the
most stable?