Chapter 10

Practice Exercises

10.1 SeF6 should have an octahedral shape (Figure 10.4) because it has six electron pairs around the central
atom.

10.2 SbCl5 should have a trigonal bipyramidal shape (Figure 10.4) because, like PCl5, it has five electron pairs
around the central atom.

10.3 HArF should have a linear shape (Figure 10.7) because although it has five electron pairs around the central
Ar atom, only two are being used for bonding.

10.4 IBr2− should have a linear shape (Figure 10.7) because although it has five electron pairs around the central
I atom, only two are being used for bonding.

10.5 RnF4 should have a square planar shape (Figure 10.10) because although it has six electron pairs around the
central Xe atom, only four are being used for bonding.

10.6 In SO32–, there are three bond pairs and one lone pair of electrons at the sulfur atom, and as shown in Figure
10.5, this ion has a trigonal pyramidal shape.

In PbCl4, there are four bonding domains (4 single bonds) around the lead atom, and as shown in
Figure10.4, this molecule has a tetrahedral shape.

In XeO4, there are four bond pairs of electrons around the Xe atom, and as shown in Figure 10.5, this
molecule is tetrahedral.

In OF2, there are two bond pairs and two lone pairs of electrons around the oxygen atom, and as shown in
Figure 10.5, this molecule is bent.

10.7 SF4 is distorted tetrahedral and has one lone pair of electrons on the sulfur, therefore it is polar.

10.8 (a) TeF6 is octahedral, and it is not polar.

(b) SeO2 is bent, and it is polar.
(c) BrCl is polar because there is a difference in electronegativity between Br and Cl.
(d) AsH3, like NH3, is pyramidal, and it is polar.
(e) CF2Cl2 is polar, because there is a difference in electronegativity between F and Cl.

10.9 The H–Cl bond is formed by the overlap of the half–filled 1s atomic orbital of a H atom with the half–filled
3p valence orbital of a Cl atom:
Cl atom in HCl (x = H electron):

x
3s 3p

The overlap that gives rise to the H–Cl bond is that of a 1s orbital of H with a 3p orbital of Cl:

10.10 The half–filled 1s atomic orbital of each H atom overlaps with a half–filled 3p atomic orbital of the P atom,
to give three P–H bonds. This should give a bond angle of 90°.
P atom in PH3 (x = H electron):

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x x x
3s 3p

The orbital overlap that forms the P–H bond combines a 1s orbital of hydrogen with a 3p orbital of
phosphorus (note: only half of each p orbital is shown):

10.11 BF3 uses sp2 hybridized orbitals since it has only three bonding electron pairs and no lone pairs of
electrons.
The sp2 hybrid orbitals on the B, x = F electron

x x x
2p
sp 2

10.12 BeF2 uses sp hybridized orbitals since it has only two bonding electron pairs and no lone pairs of electrons.
The sp hybrid orbitals on the Be; x = F electron
x x
2p
sp

10.13 sp3

x x x x
3
sp

10.14 Since there are five bonding pairs of electrons on the central phosphorous atom, we choose sp3d
hybridization for the P atom. Each of phosphorous’s five sp3d hybrid orbitals overlaps with a 3p atomic
orbital of a chlorine atom to form a total of five P–Cl single bonds. Four of the 3d atomic orbitals of P
remain unhybridized.

10.15 VSEPR theory predicts that AsCl5 will be trigonal bipyramidal. Since there are five bonding pairs of
electrons on the central arsenic atom, we choose sp3d hybridization for the As atom as a trigonal bipyramid.
Each of arsenic's five sp3d hybrid orbitals overlaps with a 3p atomic orbital of a chlorine atom to form a
total of five As–Cl single bonds. Four of the 4d atomic orbitals of As remain unhybridized.

10.16 sp3d2

10.17 (a) PCl3 has four pair of electrons around the central atom, P, so the hybridization is sp3
(b) BrCl3 has five pair of electrons around the central atom, Br, so the hybridization is sp3d

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10.18 NH3 is sp3 hybridized. Three of the electron pairs are use for bonding with the three hydrogens. The fourth
pair of electrons is a lone pair of electrons. This pair of electrons is used for the formation of the bond
between the nitrogen of NH3 and the hydrogen ion, H+.

10.19 Since there are six bonding pairs of electrons on the central phosphorous atom, we choose sp3d2
hybridization for the P atom. Each of phosphorus’s six sp3d2 hybrid orbitals overlaps with a 3p atomic
orbital of a chlorine atom to form a total of six P–Cl single bonds. Three of the 3d atomic orbitals of P
remain unhybridized.
P atom in PCl6– (x = Cl electron):

x x x x x x 3d
sp3 d 2

The ion is octahedral because six atoms and no lone pairs surround the central atom.

10.20 Atom 1has three electron domains: sp2 Atom 2 has four electron domains: sp3
2
Atom 3 has three electron domains: sp
There are 10 σ bonds and 2 π bonds in the molecule.

10.21 Atom 1has two electron domains: sp Atom 2 has three electron domains: sp2
3
Atom 3 has four electron domains: sp
There are 9 σ bonds and 3 π bonds in the molecule.

10.22 CN– has 10 valence electons and the MO diagram is similar to that of C and N. The bond order of the ion is
3 and this does agree with the Lewis structure.
σ∗2pz

π∗ 2px π∗ 2spy

σ2pz

π2px π2py

σ∗2s

σ2s

10.23 NO has 11 valence electrons, and the MO diagram is similar to that shown in Table 10.1 for O2, except that
one fewer electron is employed at the highest energy level

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σ∗2pz

π∗ 2px π∗ 2spy

π2px π2py

σ2pz

σ∗2s

σ2s

Bond Order =
(8 bonding e ) − (3 antibonding e ) = 5
− −

2 2
The bond order is calculated to be 5/2.

Review Questions

10.1 (a) See Figure 10.4. The angles are 120°.

(b) See Figures 10.4 and 10.5 The bond angles are 109.5°.
(c) See Figures 10.4 and 10.10. The bond angles are 90°.
10.2 (a) See Figure 10.4. The bond angle is 180°.
(b) See Figures 10.4 and 10.7. The bond angles are 120° between the equatorial bonds and 180°
between the two axial bonds.

10.3 VSEPR Theory is based on the principle that adjacent electron pairs repel one another, and that these
destabilizing repulsions are reduced to a minimum when electron pairs stay as far apart as possible.

10.4 An electron domain is a region in space where electrons can be found.

10.5 In HCHO, there are three bonding domains around the C; one bonding domain around each H, and one
bonding domain around O and two nonbonding domains around O.

10.6 (a) 90° bond angles

(b) 120° bond angle between equatorial bonds and 180° bond angle between axial bonds

(c) 90° bond angles between equatorial bonds and 90° bond angles between equatorial bonds and
axial bond

10.7 (a) Planar triangular, otherwise known as trigonal planar

(b) Octahedral
(c) Tetrahedral
(d) Trigonal bipyramidal

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10.8 Polar molecules attract one another, and that influences the physical and chemical properties of substances.

10.9 A bond's dipole moment is depicted with an arrow having a + sign on one end, where the "barb" of the
arrow is taken to represent the location of the opposing negative charge of the dipole:

10.10 A molecule will be polar if the bonds are polar and these polar bonds are arranged in such a geometry that
they do not cancel one another.

10.11 A molecule having polar bonds will be nonpolar only if the bond dipoles are arranged so as to cancel one
another's effect.

10.12
O O
S

The individual bond dipoles do not cancel one another.

10.13 Both VB and MO theory have wave mechanics as their theoretical basis. In each theory, bonds are
considered to arise from the overlap of orbitals. Valence bond theory uses the overlap of atomic orbitals
while molecular orbital theory uses the molecular orbitals to describe the bonding.

10.14 Lewis structures do not explain how atoms share electrons, nor do they explain why molecules adopt
particular shapes. Also, electrons are known to be delocalized, a fact which only MO theory addresses
from the beginning. Also, odd-electron systems can be more effectively discussed with MO theory.

10.15 VB theory views atoms coming together with their orbitals already containing specific electrons. The
bonds that are formed according to VB theory do so by the overlap of orbitals on neighboring atoms, and
this is accompanied by the pairing (sharing) of the electrons that are contained in the orbitals.

MO theory, on the other hand, considers a molecule to be a collection of positive nuclei surrounded by a set
of molecular orbitals, which, by definition, belong to the molecule as a whole, rather than to any specific
atom. The electrons of the molecule are distributed among the molecular orbitals according to the same
rules that govern the filling of atomic orbitals.

10.16 Orbital overlap occurs when orbitals from different atoms share the same space. This overlap provides a
more stable region for the electrons, which find themselves under the stabilizing influence of the positive
charge of two nuclei.

10.17 The greater the orbital overlap the greater the bond energy.

10.18 This is the same as the HF molecule, shown in Figure 10.16. A half–filled valence p orbital of Br overlaps
with the half–filled 1s orbital of the hydrogen atom.

10.19 Hybrid orbitals provide better overlap than do atomic orbitals, and this results in stronger bonds.

10.20 These are shown in Figures 10.21.

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10.21 sp3d sp3d2

10.22 Elements in period 2 do not have a d subshell in the valence level.

10.23 Lewis structures are something like shorthand representations of VB descriptions of molecules.

10.24 The VSEPR model gives the shape of the electron domains around the central atom; this information is
used to predict the hybridization of the atom.

10.25 90°

10.26 sp3 C atom

sp3 N atom

sp3 O atom

There are zero, one and two lone pairs, respectively, on these atoms when sp3 hybridization is utilized to
form bonds.

10.27 (a)
H

c
H
H H
(b)

N
H
H H
(c)

O
H
H

10.28 This angle would have had to be 90°, the angle between one atomic p orbital and another.

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10.29 See Figure 10.25. See Figure 10.33

Valence shell for boron Valence shell for carbon

2s 2p 2s 2p

sp2 hybridized boron atom sp2 hybridized carbon atom

sp2 2p sp2 2p

10.30 sp3d – trigonal bipyramid sp3d2 – octahedral

10.31 The ammonium ion has a tetrahedral geometry, with bond angles of 109.5°.
+
H

N
H
H H

10.32 The geometry of the boron BCl3 is trigonal planar; after the addition of the water molecule, it becomes
tetrahedral. The hybridization changes from sp2 to sp3. The geometry of the oxygen in the water molecule
changes from bent to trigonal pyramidal after coordination to the boron atom. Its hybridization does not
change, but remains at sp3.

10.33 σ bond – The electron density is concentrated along an imaginary straight line joining the nuclei of the
bonded atoms.

π bond – The electron density lies above and below an imaginary straight line joining the bonded nuclei.
10.34 The characteristic side–to–side overlap of p atomic orbitals that characterizes π bonds is destroyed upon
rotation about the bond axis. This is not the case for a σ bond, because regardless of rotation, a σ bond is
still effective at overlap.

10.35 See Figure 10.33.

10.36 See Figure 10.35.

10.37 Two resonance hybrids should be drawn.

sp2 hybrid orbitals are used for each carbon atom. Consequently, each bond angle is 120°. See Figure 9.42.

10.38 If an electron is forced to occupy the higher energy MO, the molecule loses stability and the bond is made
weaker than if an electron, or a pair of electrons, occupies the lower energy (bonding) MO.

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10.39 The overlap will create a bonding MO.

10.40 There are two regions of overall between the two 3d orbitals so this forms a π orbital.

10.41 In the hypothetical molecule He2, both the bonding and the antibonding MO are doubly occupied, and the
net bond order is zero, as shown in Figure 10.39. H2 has a bond order of 1

10.42 As shown in Table 9.1, the highest energy electrons in dioxygen occupy the doubly degenerate π–
antibonding level:

↑ ↑
π*2p x π*2p y

Since their spins are unpaired, the molecule is paramagnetic.

10.43 As shown in Table 10.1, the bond order of Li2 is 1.0. The bond order of Be2 would be zero. Yes, Be2+
could exist since the bond order would be 1/2.

10.44 (a) 2.5 (b) 1.5 (c) 1.5

10.45 As bond order increases, bond energy (and strength) increases.

10.46 See Figure 10.40.

10.47 A delocalized MO is one that extends over more than two nuclei. Benzene is planar and each carbon atom
has a half-filled p orbital perpendicular to the plane of the molecule. These orbitals overlap to form a pi
bonding system throughout the molecule.

10.48 Delocalization increases stability.

10.49 Delocalization energy is a term used in MO theory to mean essentially the same thing as the term resonance
energy, which derives from VB theory. They both represent the additional stability associated with a
spreading out of electron density.

10.50 For conductors, metals, the valence band and the conduction band are the same so electrons can easily
move throughout the metal.

For insulators, non-metals, the valence band is filled and the gap between the valence band and conduction
band is very large so electrons cannot move into the conduction band.

For semiconductors, the valence band is filled but the separation between the valence band and the
conduction band is small so electrons can easily be promoted into the conduction.

10.51 The band containing the valence electrons of the element is called the valence band.

The conduction band is the empty or partial filled band existing throughout the element.

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10.52 Increasing the temperature of a semiconductor excites more electrons from the valence band into the
conduction band.

10.53 The 2s band is completely filled and much lower in energy than the conduction band. It is not possible to
excite electrons from the 2s band into the conduction band. Calcium’s valence band is formed from the 4s
electrons and therefore, it is that band that conducts electrons.

10.54 p- type transistors are those formed by doping silicon with elements containing three valence electrons, the
3A family of elements. The doping creates a site with a positive “hole.” It is the movement of the “hole”
throughout the semiconductor that results in current flow.

An n-type transistor if formed by doping silicon with elements containing five valence electrons, the 5A
family of elements. Doping results in an extra electron at the doping site. This electron can move into the
conduction band and cause current flow.

10.55 Any element in the 3A family such as boron or gallium would form a p-type germanium transistor.

Any element in the 5A family such as phosphorus or arsenic would form an n-type germanium transistor.

10.56 A solar cell operates on the principle that light falling on the cell disturbs the equilibrium of the p-n
junction causing a flow of current.

LEDs operate on the opposite principle of a solar cell. That is, a current flows through the p-n junction
causing an emission of light.

10.57 Of the nonmetals, only the noble gases exist in nature as isolated atoms.

10.58 Period 2 elements form strong π bonds because the atom size is small which enables atoms to approach
each other very closely. Period 3 elements (and all other elements) are too large to accommodate the close
proximity required to form strong π bonds. Because the period 3 and higher elements are large and form
only weak π bonds, it is much more effective to form only σ bonds than to form a σ bond and a π bond.

10.59 Because the halogens need only a single electron to complete their valence shell, these elements do not
require the formation of π bonds. The formation of a single σ bond creates an extremely stable diatomic
molecule.

10.60 An allotrope is a different structure or physical form of an element. An isotope is a form of an atom that
differs from other atoms of the same element in the number of neutrons in the nucleus. An example is H
and D, two of the isotopes of hydrogen.

10.61 The allotropes of oxygen are dioxygen, O2, and ozone, O3.

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10.62 The two unpaired electrons are located in the π antibonding molecular orbitals.
σ2px*

π2py*, π 2pz*

π2py, π 2pz

σ2px

σ2s*

σ2s

The overall bond order is (8Be– – 4ABe–)/2 = 2.

10.63

O O O

The molecule is nonlinear and uses sp2 hybrid orbitals. There is a lone pair of electrons on the central
oxygen, consequently, ozone is indeed a polar molecule. Additionally, the formal charges suggest that O3 is
polar.

10.64 The presence of ozone in the upper atmosphere shields the earth from harmful ultraviolet
radiation.
10.65 Diamond is a network covalent solid in which each carbon atom is the corner of a tetrahedron. Each carbon
atom is bonded to four other carbon atoms using sp3 hybrid orbitals.

10.66 Graphene is a monolayer of graphite and is formed by the overlap of neighboring 2p orbitals to form a π-
type bonding throughout the layer.

Carbon forms sheets of sp2 – sp2 sigma (σ) bonds.

10.67 The weak π bonds that exist between the sheets of sp2 bonded carbon are easily broken. The lubricating
properties of graphite are a result of the weak attraction between parallel sheets.

10.68 C60, or buckminsterfullerene, resembles a soccer ball. It consists of hexagonal and pentagonal arrangements
of carbon atoms. This arrangement naturally assumes a spherical geometry. The molecule is named in
honor of R. Buckminster Fuller, an architect. Other roughly spherical arrangements of carbon atoms are
also possible. While not perfectly spherical, they resemble buckminsterfullerene and are given the general
name of fullerenes.

10.69 Carbon nanotubes have the same molecular structure as graphite, but instead of forming sheets, the layer of
carbon curves and forms a tube.

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10.70 S8

10.71 White phosphorous, P4, is a tetrahedron. See Figure 10.53

10.72 The bond angle in P4 is 60°. Using only p orbitals, a bond angle of 90° is expected. Because the observed
bond angle is much less, the molecule is extremely reactive.

10.73 Red phosphorus consists of tetrahedra joined as in Figure 10.54. While it too is used in explosives, it is
much less reactive than white phosphorus.

10.74 Black phosphorus, like graphite, exists as parallel sheets of atoms.

10.75 Silicon has a molecular structure identical to diamond, i.e., a network covalent solid arranged in a
tetrahedral manner. Silicon, unlike carbon, does not form multiple bonds. Consequently, there is no
graphite-like allotrope of silicon.

Review Problems

10.76 (a) Bent (central N atom has two single bonds and two lone pairs)
(b) Planar triangular (central C atom has three bonding domains—a double bond and two single
bonds)
(c) T-shaped (central I atom has three single bonds and two lone pairs)
(d) Linear (central Br atom has two single bonds and three lone pairs)
(e) Planar triangular (central Ga atom has three single bonds and no lone pairs)

10.77 (a) trigonal pyramidal (b) tetrahedral

(c) tetrahedral (d) nonlinear (bent)
(e) linear

10.78 (a) Bent (central F atom has four electron domains; two are lone pair)
(b) Trigonal bipyramidal (central As atom has five electron domains)
(c) Trigonal pyramidal (central As atom has four electron domains; one is a lone pair)
(d) Trigonal pyramidal (central Sb atom has four electron domains; one is a lone lair)
(e) Bent (central Se atom has four electron domains; two are lone pair)

10.79 (a) distorted tetrahedral (b) octahedral

(c) nonlinear (d) tetrahedral
(e) tetrahedral

10.80 (a) Tetrahedral (central I atom has four electron domains)

(b) Square planar (central I atom has six electron domains; two are lone pair)
(c) Octahedral (central Te atom has six electron domains)
(d) Tetrahedral (central Si atom has four electron domains)
(e) Linear (central I atom has five electron domains; three are lone pair)

10.81 (a) linear (b) square planar

(c) T–shaped (d) trigonal pyramidal

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(e) planar triangular

10.82 PF4− The central P atom has five electron domains, one is a lone pair

10.83 AsH3

10.84 180° There are two electron domains around each carbon atom so the molecule is linear

10.85 all angles 120°

10.86 (a) 109.5° (b) 109.5°

(c) 120° (d) 180°
(e) 109.5°

10.87 (a) 90° (b) 109.5°

(c) 180° (d) 109.5°
(e) 109.5°

10.88 The ones that are polar are (a), (b), and (c). The last two have symmetrical structures, and although
individual bonds in these substances are polar bonds, the geometry of the bonds serves to cause the
individual dipole moments of the various bonds to cancel one another.

10.89 I3− contains no polar bonds. BeCl2 is linear so the individual dipoles cancel each other. C2H6 has atoms
symmetrically distributed and is non-polar. SO2 and SbCl52− both have a lone pair of electrons and have a
bent shape and square pyramid shape respectively, and are therefore polar molecules.

10.90 All are polar. (a), (b), (c) and (e) have asymmetrical structures, and (d) only has one bond, which is polar.

10.91 OH− is linear and polar. Each of the other structures have one or more lone pairs on the central atom and
are therefore polar.

10.92 In SF6, although the individual bonds in this substance are polar bonds, the geometry of the bonds is
symmetrical which serves to cause the individual dipole moments of the various bonds to cancel one
another. In SF5Br, one of the six bonds has a different polarity so the individual dipole moments of the
various bonds do not cancel one another.

10.93 In SiCl4, although the individual bonds in this substance are polar bonds, the geometry of the bonds is
symmetrical which serves to cause the individual dipole moments of the various bonds to cancel one
another. In SiHCl3, one of the four bonds has a different polarity so the individual dipole moments of the
various bonds do not cancel one another.

10.94 The 1s atomic orbitals of the hydrogen atoms overlap with the mutually perpendicular p atomic orbitals of
the selenium atom.

Se atom in H2Se (x = H electrons):

x x
4s 4p

10.95 This is shown in Figure 10.18 for F2 . Since Cl2 is in the same family the bonding will be similar, using the
n = 3 shell rather than the n = 2 shell. We can diagram it showing the orbitals of one of the chlorine atoms:
Each Cl atom (x = an electron from the other Cl atom):

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10.96 Atomic B:

2s 2p
Hybridized B: (x = a Cl electron)

10.97 (a) Si atom in SiCl4 (x = a Cl electron)

x x x x
3
sp

(b) P atom in PCl5 (x = a Cl electron)

x x x x x
3 3d
sp d

10.98 (a) There are three bonds to the central Cl atom, plus one lone pair of electrons. The geometry of the
electron pairs is tetrahedral so the Cl atom is to be sp3 hybridized:

_
O

O Br

(b) There are two atoms bonded to the central selenium atom, and one lone pair on the central
selenium. The geometry of the electron pairs is that of a planar triangle, and the hybridization of
the Se atom is sp2:

O Se O

One other resonance structure should also be drawn for SeO2.

(c) There are two bonds to the central S atom, as well as two lone pairs. The S atom is to be sp3
hybridized, and the geometry of the electron pairs is tetrahedral.

Cl S Cl

10.99 (a) Five Cl atoms and one pair of electrons surround the central Sb atom in an octahedral geometry,
and the hybridization of Sb is sp3d2.

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Cl Cl
Sb
Cl Cl
Cl

(b) Four Br atoms are bonded to the Se atom, plus the Se atom has a lone pairs of electrons. This
requires the Se atom to be sp3d hybridized, and the geometry is a see-saw.

Br

Br Se Br

Br

(c) The central B atom is bonded to three F atoms. The molecule has trigonal planar geometry. This
requires sp3 hybridization of B.

B F

10.100 (a) There are three bonds to As and one lone pair at As, requiring As to be sp3 hybridized.

The Lewis diagram

Cl As Cl

Cl
The hybrid orbital diagram for As: (x = a Cl electron)

x x x
sp 3

(b) There are three atoms bonded to the central Cl atom, and it also has two lone pairs of electrons.
The hybridization of Cl is thus sp3d.

The Lewis diagram

F Cl F

F
The hybrid orbital diagram for Cl: (x = a F electron)

x x 3d
sp 3d

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10.101 (a) Sb has three bonds to Cl atoms and two lone pairs and is therefore sp3d hybridized.

The Lewis diagram

The hybrid orbital diagram for Sb: (x = a Cl electron)

(b) Se has two bonds to Cl atoms and two lone pairs of electrons, requiring it to be sp3 hybridized.

The Lewis diagram

Se
Cl Cl
The hybrid orbital diagram for Se: (x = a Cl electron)

x x
sp

10.102 We can consider that this ion is formed by reaction of SbF5 with F–. The antimony atom accepts a pair of
electrons from fluoride:
Sb in SbF6–: (xx = an electron pair from the donor F–)

xx
sp 3d 2

10.103 This is an octahedral ion with sp3d2 hybridized tin:

Sn atom in SnCl62– (xx = an electron pair from the donor Cl–)

x x x x xx xx 3d
3 2
sp d

10.104 (a) N in the C=N system:

2p
2
sp

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2p
sp2

sp2
sp2

(b) sigma bond pi bond

C N

C N

(c)
H 120 o

120 o C N

H 120 o H
120o

10.105 (a) sp– hybridized N atom:

2p
sp

(b) The σ bonds:

C N
The π bonds:

C N

(c) For HCN, the only difference from (b) is the formation of another σ bond when an H 1s orbital
overlaps the C sp hybrid orbital.

(d) The HCN bond angle should be 180°.

10.106 Each carbon atom is sp2 hybridized, and each C–Cl bond is formed by the overlap of an sp2 hybrid of
carbon with a p atomic orbital of a chlorine atom. The C=C double bond consists first of a C–C σ bond
formed by "head on" overlap of sp2 hybrids from each C atom. Secondly, the C=C double bond consists of
a side–to–side overlap of unhybridized p orbitals of each C atom, to give one π bond. The molecule is
planar, and the expected bond angles are all 120°.

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10.107 The central carbon uses sp2 orbitals to bond to the hydrogen s orbitals and the oxygen sp2 orbitals.

10.108 1. sp3 2. sp 3. sp2 4. sp2

10.109 1. one σ bond

2. one σ bond and two π bonds
3. one σ bond
4. This requires sp2 hybridization of B.

10.110 Here we pick the one with the higher bond order.

(a) O 2+ (b) O2 (c) N2

10.111 NO has 11 valence electrons, and the MO diagram is similar to that shown in Table 10.1 for O2, except that
one fewer electron is employed at the highest energy level
The bond order for NO is calculated to be 5/2:

Bond Order =
(8 bonding e ) − (3 antibonding e ) = 5
− −

2 2
If we remove one electron to form NO+, the bond order becomes 3 (there are only two antibonding
electrons). The larger bond order indicates a shorter bond length.

10.112 (a) N 2+ (b) NO (c) O 2–

10.113 All of the molecules or ions are paramagnetic except N2.

10.114
σ∗s

1s

2p
2p

σs

2s
2s
Hydrogen Oxygen
There are two electrons in bonding MOs and three electrons in nonbonding MOs.
The net bond order is 1.

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10.115
B σ∗p N

2p π∗ p

2p

σp

πp

σ∗s
2s
2s
σs
The molecule would be diamagnetic and the net bond order in the molecule would be 2.0.

Additional Exercises

10.116 planar triangular

10.117 Five valence electrons
Group VA

X
Cl
Cl
Cl
Three valence electrons
Group IIIA
Cl

X
Cl Cl

Seven valence electrons
Group VIIA

Cl

X Cl

Cl
It is unlikely that X would be in Group VI because it would have an unpaired electron since X would have
six valence electrons and three would be used for bonding with the Cl, and that would leave three
remaining electrons.

10.118 Since the angles are nearer to 90° than to 109°, we must use atomic rather than hybrid orbitals on antimony.

10.119 (a) planar triangular
tetrahedral

(b) trigonal bipyramidal
octahedral
(c) T-shaped
square planar
(d) Trigonal pyramidal
trigonal bipyramidal
(e) linear
planar

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10.120 Structure (a)

10.121 The normal C–C–C angle for an sp3 hybridized carbon atom is 109.5°. The 60° bond angle in
cyclopropane is much less than this optimum bond angle. This means that the bonding within the ring
cannot be accomplished through the desirable "head on" overlap of hybrid orbitals from each C atom. As a
result, the overlap of the hybrid orbitals in cyclopropane is less effective than that in the more normal,
noncyclic propane molecule, and this makes the C–C bonds in cyclopropane comparatively weaker than
those in the noncyclic molecule. We can also say that there is a severe "ring strain" in the molecule.

10.122 (a) PF3 is a pyramidal molecule and uses sp3 hybrid orbitals. The expected bond angle is 109.5°.
(b) Using the unhybridized p orbitals, we would anticipate a bond angle of 90°.
(c) The observed bond angle is almost exactly the average of the bond angles listed in parts (a) and (b)
above. So, neither hybrid orbitals nor unhybridized atomic orbitals explain the observed bond
angle.

10.123 The arrangement around an sp2 hybridized atom may have 120° bond angles (which well accommodates a
six–membered ring, the geometrical arrangement around an atom that is sp hybridized must be linear, as in
C – C ≡ C – C systems.

10.124 The arrangement of the atoms is trigonal bipyramidal.

Recall that the bond angle between equatorial atoms is 120°. The bond angle from the equatorial position to
the axial position is 90°. Due to the smaller bond angles, the atoms in the axial positions create more
repulsions. The structure with the least amount of total repulsion is preferred; the statement implies that the
more electronegative atoms create less repulsion; therefore the more electronegative atom should be placed
in the axial position. Since fluorine is more electronegative than chlorine, the F atoms will be in the axial
positions and the Cl atoms will be in the equatorial positions. The molecule is non–polar.
F

Cl
Cl P
Cl
F

10.125 The lone pair of electrons repels the Te–F bonding pairs, causing the F–Te–F angles to be smaller than in
the ideal trigonal bipyramid.

This angle less than 180 o

F
Te
This angle less than 120o

In BrF5, the lone pair is located perpendicular to the plane made up of four of the F atoms , giving a square
pyramid geometry to the molecule. The angle between the four F in the plane and the f above the plane will
be less than 900 due to lone pair repulsion. The F-Br-F angles in the plan will remain 900.

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10.126 The double bonds are predicted to be between S and O atoms. Hence, the Cl–S–Cl angle diminishes under
the influence of the S=O double bonds.

O
strong repulsion

S
O
Cl
Cl

weak repulsion

10.127 This is a π bond, since overlap is side to side rather than the end to end. Also, consider that no bond
rotation is possible here without breaking the bond since overlap occurs both above and below the bond
axis.

The diagrams below show bonding and antibonding combinations, respectively.

10.128 Only the px orbital can form a π bond with dxz, if the internuclear axis is the z axis.

Multi-Concept Problems

10.129 (a) The O–O–N bond angle is about 109.5° and the O–N–O bond angle is around 120°.
(b) sp2

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(c) The nitrate ion benefits from three stable resonance structures (or electron delocalization) which
stabilize it. The peroxynitrite ion does not.

10.130 The polarity in the N–H bond, as measured by the difference in electronegativities between N (3.1) and H
(2.1) adds to the polarity created by the sp3 hybridized lone pair on the N atom. However, the higher
electronegativity of fluorine (4.1) causes the N–F bond polarity to oppose the polarity associated with the
hybridized lone pair on the N atom. Thus in the first case, a net dipole exists in the molecule, whereas in
the second case, the polarity of the N–F bonds cancel the polarity of the hybrid lone pair.

10.131 (a) The C–C single bonds are formed from head–to–head overlap of C atom sp2 hybrids. This leaves
one unhybridized atomic p orbital on each carbon atom, and each such atomic orbital is oriented
perpendicular to the plane of the molecule.

(b) Sideways or π type overlap is expected between the first and the second carbon atoms, as well as
between the third and the fourth carbon atoms. However, since all of these atomic p orbitals are
properly aligned, there can be continuous π type overlap between all four carbon atoms.

(d) The situation described in part (b) is delocalized. We expect completely delocalized π type
bonding among the carbon atoms. Therefore, the center C-C bond has some π character and is thus
shorter than a normal C-C single bond.

10.132 The compound is of the form PnBrm. From the mass of AgBr formed we can determine the mass of Br in
the original compound. The mass of Br will also allow the determination of the number of moles of Br in
the phosphorus compound. Then, using the original mass of the phosphorus compound, we can determine
the mass and moles of P. Using this information , we can determine the empirical formula of the
compound.
1mol AgBr 1 mol Br
0.508 g AgBr x x = 2.705 x 10−3 mol Br
187.77 g mol AgBr

−3 79.904 g
Grams of Br = 2.705 x 10 mol Br x = 0.216
mol

Grams of P = 0.244 g Pm Brn - 0.216 g Br = 0.028 g

1 mol P
Moles of P = 0.028 g P x = 8.98 x 10−4
30.97 g

Empirical formula:

P0.000898 Br0.002705 or PBr3

Since P has five valence electrons, forming PBr3 results in three P-Br bonds and a lone-pair of electrons on
P. The geometry of the compound is trigonal pyramid and the hybridization is sp3. Since the P-Br bonds are
polar the geometry of PBr3 results in a polar molecule.

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