Sample Exercise 9.
1 Using the VSEPR Model
Use the VSEPR model to predict the molecular geometry of (a) O3, (b) SnCl3–.
Solution
Analyze We are given the molecular formulas of a molecule and a polyatomic ion, both conforming to the general
formula ABn and both having a central atom from the p block of the periodic table. (Notice that for O3, the A and B
atoms are all oxygen atoms.)
Plan To predict the molecular geometries, we draw their Lewis structures and count electron domains around the
central atom to get the electron-domain geometry. We then obtain the molecular geometry from the arrangement of the
domains that are due to bonds.
Solve
(a) We can draw two resonance structures for O3:
Because of resonance, the bonds between the central O atom
and the outer O atoms are of equal length. In both resonance
structures, the central O atom is bonded to the two outer
O atoms and has one nonbonding pair. Thus, there are three
electron domains about the central O atoms. (Remember that
a double bond counts as a single electron domain.) The
arrangement of three electron domains is trigonal planar
(Table 9.1). Two of the domains are from bonds, and one is
due to a nonbonding pair. So, the molecular geometry is bent
with an ideal bond angle of 120° (Table 9.2).
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Sample Exercise 9.1 Using the VSEPR Model
Continued
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Sample Exercise 9.1 Using the VSEPR Model
Continued
Comment As this example illustrates, when a molecule exhibits resonance, any one of the resonance structures can be
used to predict the molecular geometry.
(b) The Lewis structure for SnCl3– is:
The central Sn atom is bonded to the three Cl atoms and has one nonbonding pair; thus, we have four electron
domains, meaning a tetrahedral electrondomain geometry (Table 9.1) with one vertex occupied by a nonbonding
pair of electrons. A tetrahedral electron-domain geometry with three bonding and one nonbonding domains leads to
a trigonal-pyramidal molecular geometry (Table 9.2).
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Sample Exercise 9.1 Using the VSEPR Model
Continued
Practice Exercise
Predict the electron-domain and molecular geometries for
(a) SeCl2, (b) CO32–.
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Sample Exercise 9.2 Molecular Geometries of Molecules with
Expanded Valence Shells
Use the VSEPR model to predict the molecular geometry of (a) SF4, (b) IF5.
Solution
Analyze The molecules are of the ABn type with a central p-block atom.
Plan We first draw Lewis structures and then use the VSEPR model to determine the electron-domain geometry and
molecular geometry.
Solve
(a) The Lewis structure for SF4 is:
The sulfur has five electron domains around it: four from the S — F
bonds and one from the nonbonding pair. Each domain points toward a
vertex of a trigonal bipyramid. The domain from the nonbonding pair
will point toward an equatorial position. The four bonds point toward
the remaining four positions, resulting in a molecular geometry that is
described as seesaw-shaped:
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Sample Exercise 9.2 Molecular Geometries of Molecules with
Expanded Valence Shells
Continued
Comment The experimentally observed structure is shown on the right. We can infer
that the nonbonding electron domain occupies an equatorial position, as predicted. The
axial and equatorial S — F bonds are slightly bent away from the nonbonding domain,
suggesting that the bonding domains are “pushed” by the nonbonding domain, which
exerts a greater repulsion (Figure 9.7).
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Sample Exercise 9.2 Molecular Geometries of Molecules with
Expanded Valence Shells
Continued
Solve
(b) The Lewis structure of IF5 is:
The iodine has six electron domains around it, one of
which is nonbonding. The electron-domain geometry is
therefore octahedral, with one position occupied by the
nonbonding pair, and the molecular geometry is square
pyramidal (Table 9.3):
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Sample Exercise 9.2 Molecular Geometries of Molecules with
Expanded Valence Shells
Continued
Comment Because the nonbonding domain is larger than the bonding domains, we predict that the four F atoms in
the base of the pyramid will be tipped up slightly toward the top F atom. Experimentally, we find that the angle
between the base atoms and the top F atom is 82°, smaller than the ideal 90° angle of an octahedron.
Practice Exercise
A certain AB4 molecule has a square-planar molecular geometry. Which of the following statements about the
molecule is or are true?
(i) The molecule has four electron domains about the central atom A.
(ii) The B — A — B angles between neighboring B atoms are 90°.
(iii)The molecule has two nonbonding pairs of electrons on atom A.
(a) Only one of the statements is true.
(b) Statements (i) and (ii) are true.
(c) Statements (i) and (iii) are true.
(d) Statements (ii) and (iii) are true.
(e) All three statements are true.
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Sample Exercise 9.3 Predicting Bond Angles
Eyedrops for dry eyes usually contain a water-soluble polymer called poly(vinyl alcohol), which is based on the
unstable organic molecule vinyl alcohol:
Predict the approximate values for the H — O — C and O — C — C bond angles in vinyl alcohol.
Solution
Analyze We are given a Lewis structure and asked to determine two bond angles.
Plan To predict a bond angle, we determine the number of electron domains surrounding the middle atom in the
angle. The ideal angle corresponds to the electron-domain geometry around the atom. The angle will be compressed
somewhat by nonbonding electrons or multiple bonds.
Solve In H — O — C, the O atom has four electron domains (two bonding, two nonbonding). The electron-domain
geometry around O is therefore tetrahedral, which gives an ideal angle of 109.5°. The H — O — C angle is
compressed somewhat by the nonbonding pairs, so we expect this angle to be slightly less than 109.5°.
To predict the O — C — C bond angle, we examine the middle atom in the angle. In the molecule, there are three
atoms bonded to this C atom and no nonbonding pairs, and so it has three electron domains about it. The predicted
electron-domain geometry is trigonal planar, resulting in an ideal bond angle of 120°. Because of the larger size of
the C C domain, the bond angle should be slightly greater than 120°.
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Sample Exercise 9.3 Predicting Bond Angles
Continued
Practice Exercise
The atoms of the compound methylhydrazine, CH6N2, which is used as
a rocket propellant, are connected as follows (note that lone pairs are not
shown): What do you predict for the ideal values of the C — N — N
and H — N — H angles, respectively?
(a) 109.5° and 109.5° (b) 109.5° and 120° (c) 120° and 109.5°
(d) 120° and 120° (e) None of the above
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Sample Exercise 9.4 Polarity of Molecules
Predict whether these molecules are polar or nonpolar: (a) BrCl, (b) SO2, (c) SF6.
Solution
Analyze We are given three molecular formulas and asked to predict whether the molecules are polar.
Plan A molecule containing only two atoms is polar if the atoms differ in electronegativity. The polarity of a molecule
containing three or more atoms depends on both the molecular geometry and the individual bond polarities. Thus, we
must draw a Lewis structure for each molecule containing three or more atoms and determine its molecular geometry.
We then use electronegativity values to determine the direction of the bond dipoles. Finally, we see whether the bond
dipoles cancel to give a nonpolar molecule or reinforce each other to give a polar one.
Solve
(a) Chlorine is more electronegative than bromine. All diatomic molecules with polar bonds are polar molecules.
Consequently, BrCl is polar, with chlorine carrying the partial negative charge:
The measured dipole moment µ of BrCl is 0.57 D.
(b) Because oxygen is more electronegative than sulfur, SO2 has polar bonds. Three resonance forms can be written:
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Sample Exercise 9.4 Polarity of Molecules
Continued
For each of these, the VSEPR model predicts a bent molecular geometry. Because the molecule is bent, the bond
dipoles do not cancel, and the molecule is polar:
Experimentally, the dipole moment µ of SO2 is 1.63 D.
(c) Fluorine is more electronegative than sulfur, so the bond dipoles point toward fluorine. For clarity, only one S — F
dipole is shown. The six S — F bonds are arranged octahedrally around the central sulfur:
Because the octahedral molecular geometry is symmetrical, the bond dipoles cancel, and the molecule is nonpolar,
meaning that µ = 0.
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Sample Exercise 9.4 Polarity of Molecules
Continued
Practice Exercise
Consider an AB3 molecule in which A and B differ in electronegativity. You are told that the molecule has an
overall dipole moment of zero. Which of the following could be the molecular geometry of the molecule?
(a) Trigonal pyramidal
(b) Trigonal planar
(c) T-shaped
(d) Tetrahedral
(e) More than one of the above
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Sample Exercise 9.5 Describing the Hybridization of a Central Atom
Describe the orbital hybridization around the central atom in NH2–.
Solution
Analyze We are given the chemical formula for a polyatomic anion and asked to describe the type of hybrid orbitals
surrounding the central atom.
Plan To determine the central atom hybrid orbitals, we must know the electron-domain geometry around the atom.
Thus, we draw the Lewis structure to determine the number of electron domains around the central atom. The
hybridization conforms to the number and geometry of electron domains around the central atom as predicted by the
VSEPR model.
Solve The Lewis structure is
Because there are four electron domains around N,
the electrondomain geometry is tetrahedral. The
hybridization that gives a tetrahedral electron-
domain geometry is sp3 (Table 9.4). Two of the sp3
hybrid orbitals contain nonbonding pairs of
electrons, and the other two are used to make
bonds with the hydrogen atoms.
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Sample Exercise 9.5 Describing the Hybridization of a Central Atom
Continued
Practice Exercise
For which of the following molecules or ions does the following description apply? “The bonding can be explained
using a set of sp2 hybrid orbitals on the central atom, with one of the hybrid orbitals holding a nonbonding pair of
electrons.”
(a) CO2
(b) H2S
(c) O3
(d) CO32–
(e) More than one of the above
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Sample Exercise 9.6 Describing and Bonds in a Molecule
Formaldehyde has the Lewis structure
Describe how the bonds in formaldehyde are formed in terms of overlaps of hybrid and unhybridized orbitals.
Solution
Analyze We are asked to describe the bonding in formaldehyde in terms of hybrid orbitals.
Plan Single bonds are bonds, and double bonds consist of one bond and one bond. The ways in which these
bonds form can be deduced from the molecular geometry, which we predict using the VSEPR model.
Solve The C atom has three electron domains around it, which suggests a trigonal-planar geometry with bond
angles of about 120°. This geometry implies sp2 hybrid orbitals on C (Table 9.4). These hybrids are used to make
the two C — H and one C — O bonds to C. There remains an unhybridized 2p orbital on carbon, perpendicular
to the plane of the three sp2 hybrids.
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Sample Exercise 9.6 Describing and Bonds in a Molecule
Continued
The O atom also has three electron domains around it, and
so we assume it has sp2 hybridization as well. One of these
hybrid orbitals participates in the C — O bond, while the
other two hold the two nonbonding electron pairs of the O
atom. Like the C atom, therefore, the O atom has a p orbital
that is perpendicular to the plane of the molecule. The two p
orbitals overlap to form a C — O bond (Figure 9.24).
Figure 9.24 Formation of and bonds in formaldehyde, H2CO.
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Sample Exercise 9.6 Describing and Bonds in a Molecule
Continued
Practice Exercise
We have just arrived at a bonding description for the formaldehyde molecule. Which of the following statements
about the molecule is or are true?
(i) Two of the electrons in the molecule are used to make the bond in the molecule.
(ii) Six of the electrons in the molecule are used to make the bonds in the molecule.
(iii)The C — O bond length in formaldehyde should be shorter than that in methanol, H3COH.
(a) Only one of the statements is true.
(b) Statements (i) and (ii) are true.
(c) Statements (i) and (iii) are true.
(d) Statements (ii) and (iii) are true.
(e) All three statements are true.
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Sample Exercise 9.7 Delocalized Bonding
Describe the bonding in the nitrate ion, NO3–. Does this ion have delocalized bonds?
Solution
Analyze Given the chemical formula for a polyatomic anion, we are asked to describe the bonding and determine
whether the ion has delocalized bonds.
Plan Our first step is to draw Lewis structures. Multiple resonance structures involving the placement of the
double bonds in different locations would suggest that the component of the double bonds is delocalized.
Solve In Section 8.6 we saw that NO3– has three resonance structures:
In each structure, the electron-domain geometry at nitrogen is trigonal planar, which implies sp2 hybridization of
the N atom. It is helpful when considering delocalized bonding to consider atoms with lone pairs that are bonded
to the central atom to be sp2 hybridized as well. Thus, we can envision that each of the O atoms in the anion has
three sp2 hybrid orbitals in the plane of the ion. Each of the four atoms has an unhybridized p orbital oriented
perpendicular to the plane of the ion.
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Sample Exercise 9.7 Delocalized Bonding
Continued
The NO3– ion has 24 valence electrons. We can first use the sp2 hybrid orbitals on the four atoms to construct the
three N — O bonds. That uses all of the sp2 hybrids on the N atom and one sp2 hybrid on each O atom. Each of
the two remaining sp2 hybrids on each O atom is used to hold a nonbonding pair of electrons. Thus, for any of the
resonance structures, we have the following arrangement in the plane of the ion:
Notice that we have accounted for a total of 18 electrons—6 in the three N — O bonds, and 12 as nonbonding
pairs on the O atoms. The remaining six electrons will reside in the system of the ion.
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Sample Exercise 9.7 Delocalized Bonding
Continued
The four p orbitals—one on each of the four atoms—are used to build the system. For any one of the three
resonance structures shown, we might imagine a single localized N — O bond formed by the overlap of the p orbital
on N and a p orbital on one of the O atoms. The remaining two O atoms have nonbonding pairs in their p orbitals.
Thus, for each of the resonance structures, we have the situation shown in Figure 9.27. Because each resonance
structure contributes equally to the observed structure of NO3–, however, we represent the bonding as delocalized
over the three N — O bonds, as shown in the figure. We see that the NO3– ion has a six-electron system delocalized
among the four atoms in the ion.
Figure 9.27 Localized and delocalized
representations of the six-electron system
in NO3–.
Practice Exercise
How many electrons are in the system of the ozone molecule, O3? (a) 2 (b) 4 (c) 6 (d) 14 (e) 18
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Sample Exercise 9.8 Bond Order
What is the bond order of the He2+ ion? Would you expect this ion to be stable relative to the separated He atom and
He+ ion?
Solution
Analyze We will determine the bond order for the He2+ ion and use it to predict whether the ion is stable.
Plan To determine the bond order, we must determine the number of electrons in the molecule and how these
electrons populate the available MOs. The valence electrons of He are in the 1s orbital, and the 1s orbitals combine to
give an MO diagram like that for H2 or He2 (Figure 9.33). If the bond order is greater than 0, we expect a bond to
exist, and the ion is stable.
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Sample Exercise 9.8 Bond Order
Continued
Solve The energy-level diagram for the He2+ ion is shown in Figure 9.34. This ion has three electrons. Two are
placed in the bonding orbital and the third in the antibonding orbital. Thus, the bond order is
Bond order = (2 – 1) =
Because the bond order is greater than 0, we predict the He2+ ion to be stable relative to the separated He and He+.
Formation of He2+ in the gas phase has been demonstrated in laboratory experiments.
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Sample Exercise 9.8 Bond Order
Continued
Practice Exercise
How many of the following molecules and ions have a bond order of : H2, H2+, H2–, and He22+?
(a) 0 (b) 1 (c) 2 (d) 3 (e) 4
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Sample Exercise 9.9 Molecular Orbitals of a Period 2 Diatomic Ion
For the O2+ ion predict (a) number of unpaired electrons, (b) bond order, (c) bond enthalpy and bond length.
Solution
Analyze Our task is to predict several properties of the cation O2+.
Plan We will use the MO description of O2+ to determine the desired properties. We must first determine the number
of electrons in O2+ and then draw its MO energy diagram. The unpaired electrons are those without a partner of
opposite spin. The bond order is one-half the difference between the number of bonding and antibonding electrons.
After calculating the bond order, we can use Figure 9.43 to estimate the bond enthalpy and bond length.
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Sample Exercise 9.9 Molecular Orbitals of a Period 2 Diatomic Ion
Continued
Solve
(a) The O2+ ion has 11 valence electrons, one fewer than O2. The electron removed from O2 to form O2+ is one of the
two unpaired electrons (see Figure 9.43). Therefore, O2+ has one unpaired electron.
(b) The molecule has eight bonding electrons (the same as O2) and three antibonding electrons (one fewer than O2).
Thus, its bond order is
(8 – 3) = 2
(c) The bond order of O2+ is between that for O2 (bond order 2) and N2 (bond order 3). Thus, the bond enthalpy and
bond length should be about midway between those for O2 and N2, approximately 700 kJ/mol and 115 pm. (The
experimentally measured values are 625 kJ/mol and 112.3 pm.)
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Sample Exercise 9.9 Molecular Orbitals of a Period 2 Diatomic Ion
Continued
Practice Exercise
Place the following molecular ions in order from smallest to largest bond order: C22+, N2–, O2–, and F2–.
(a) C22+ < N2– < O2– < F2–
(b) F2– < O2– < N2– < C22+
(c) O2– < C22+ < F2– < N2–
(d) C22+ < F2– < O2– < N2–
(e) F2– < C22+ < O2– < N2–
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Sample Integrative Exercise Putting Concepts Together
Elemental sulfur is a yellow solid that consists of
S8 molecules. The structure of the S8 molecule is a
puckered, eight-membered ring (see Figure 7.27).
Heating elemental sulfur to high temperatures
produces gaseous S2 molecules:
S8(s) 4 S2(g)
(a) The electron configuration of which period 2
element is most similar to that of sulfur? (b) Use
the VSEPR model to predict the S — S — S bond
angles in S8 and the hybridization at S in S8. (c)
Use MO theory to predict the sulfur–sulfur bond
order in S2. Do you expect this molecule to be
diamagnetic or paramagnetic? (d) Use average
bond enthalpies (Table 8.3) to estimate the
enthalpy change for this reaction. Is the reaction
exothermic or endothermic?
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Sample Integrative Exercise Putting Concepts Together
Continued
Solution
(a) Sulfur is a group 16 element with an [Ne]3s23p4 electron configuration. It is expected to be most similar
electronically to oxygen (electron configuration, [He]2s22p4), which is immediately above it in the periodic table.
(b) The Lewis structure of S8 is
There is a single bond between each pair of S atoms and two nonbonding electron pairs on each S atom. Thus, we
see four electron domains around each S atom and expect a tetrahedral electron-domain geometry corresponding
to sp3 hybridization. Because of the nonbonding pairs, we expect the S — S — S angles to be somewhat less than
109.5°, the tetrahedral angle. Experimentally, the S — S — S angle in S8 is 108°, in good agreement with this
prediction. Interestingly, if S8 were a planar ring, it would have S — S — S angles of 135°. Instead, the S8 ring
puckers to accommodate the smaller angles dictated by sp3 hybridization.
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Sample Integrative Exercise Putting Concepts Together
Continued
(c) The MOs of S2 are analogous to those of O2, although the MOs for S2 are constructed from the 3s and 3p atomic
orbitals of sulfur. Further, S2 has the same number of valence electrons as O2. Thus, by analogy with O2, we
expect S2 to have a bond order of 2 (a double bond) and to be paramagnetic with two unpaired electrons in the
molecular orbitals of S2.
(d) We are considering the reaction in which an S8 molecule falls apart into four S2 molecules. From parts (b) and
(c), we see that S8 has S — S single bonds and S2 has S S double bonds. During the reaction, therefore, we
are breaking eight S — S single bonds and forming four S S double bonds. We can estimate the enthalpy of
the reaction by using Equation 5.33 and the average bond enthalpies in Table 8.3:
Hrxn = 8 D(S — S) – 4 D(S S)
= 8(266 kJ) – 4(418 kJ) = +456 kJ
Recall that D(X — Y) represents the X — Y bond enthalpy. Because Hrxn > 0, the reaction is endothermic
(Section 5.3). The very positive value of Hrxn suggests that high temperatures are required to cause the reaction
to occur.
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