CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

CHAPTER 4
MOLECULAR STRUCTURE AND
INTERACTION
4.1 (a) The Lewis structure of PCl3 is shown below. Since in the VSEPR method the number of bonding pairs
and lone pairs of electrons around the central atom (phosphorus, in this case) is important in determining
the structure, the lone pairs of electrons around the chlorine atoms have been omitted for simplicity.
There are three bonds and one lone electron pair around the central atom, phosphorus, which makes this
an AB3E case. The information in Table 4.2 in the text shows that the structure is a trigonal pyramid like
ammonia.

Cl P Cl
Cl
What would be the structure of the molecule if there were no lone pairs and only three bonds?

(b) The Lewis structure of CHCl3 is shown below. There are four bonds and no lone pairs around carbon
which makes this an AB4 case. The molecule should be tetrahedral like methane (Table 4.1 in the text).

H
Cl C Cl
Cl

(c) The Lewis structure of SiH4 is shown below. Like part (b), it is a tetrahedral AB 4 molecule.
H
H Si H
H

(d) The Lewis structure of TeCl4 is shown below. There are four bonds and one lone pair which make this
an AB4E case. Consulting Table 4.2 in the text shows that the structure should be that of a distorted
tetrahedron like SF4.
Cl Te Cl
Cl Cl

Are TeCl4 and SF4 isoelectronic? Should isoelectronic molecules have similar VSEPR structures?

4.2 Strategy: The sequence of steps in determining molecular geometry is as follows:

draw Lewis 
 find arrangement of 
 find arrangement 
 determine geometry
structure electrons pairs of bonding pairs based on bonding pairs

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

Solution:
Lewis structure Electron pairs Electron Lone pairs Geometry
on central atom arrangement

Cl

Cl Al Cl
(a) 3 trigonal planar 0 trigonal planar, AB3

Cl Zn Cl
(b) 2 linear 0 linear, AB2

Cl 2

Cl Zn Cl
Cl
(c) 4 tetrahedral 0 tetrahedral, AB4

4.3
Lewis Structure e pair arrangement geometry

Br
(a) tetrahedral tetrahedral
Br C Br
Br

(b) Cl B Cl trigonal planar trigonal planar

Cl

(c) F N F tetrahedral trigonal pyramidal

F
(d) tetrahedral bent
H Se H
(e)  trigonal planar bent
O N O

4.4 We use the following sequence of steps to determine the geometry of the molecules.

draw Lewis 
 find arrangement of 
 find arrangement 
 determine geometry
structure electrons pairs of bonding pairs based on bonding pairs

(a) Looking at the Lewis structure we find 4 pairs of electrons around the central atom. The electron pair
arrangement is tetrahedral. Since there are no lone pairs on the central atom, the geometry is also
tetrahedral.

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

H
H C I
H
(b) Looking at the Lewis structure we find 5 pairs of electrons around the central atom. The electron pair
arrangement is trigonal bipyramidal. There are two lone pairs on the central atom, which occupy
positions in the trigonal plane. The geometry is t-shaped.

F Cl F
F

(c) Looking at the Lewis structure we find 4 pairs of electrons around the central atom. The electron pair
arrangement is tetrahedral. There are two lone pairs on the central atom. The geometry is bent.
H S H

(d) Looking at the Lewis structure, there are 3 VSEPR pairs of electrons around the central atom. Recall
that a double bond counts as one VSEPR pair. The electron pair arrangement is trigonal planar. Since
there are no lone pairs on the central atom, the geometry is also trigonal planar.
O
O S O

(e) Looking at the Lewis structure, there are 4 pairs of electrons around the central atom. The electron pair
arrangement is tetrahedral. The geometry is trigonal pyramidal.
2
O
O S O

4.5 The lone pairs of electrons on the bromine atoms have been omitted for simplicity.

Br Hg Br N N O S C N

linear linear linear

4.6 (a) tetrahedral; (b) bent; (c) trigonal planar; (d) linear; (e) square planar; (f) tetrahedral; (g) trigonal
bipyramidal; (h) trigonal pyramidal; (i) tetrahedral.

4.7 In XeO2 the central xenon will have three lone pairs giving it a trigonal bipyramidal arrangement of electron
pairs and a linear geometry. In XeO4, the central xenon has two lone pairs of electrons giving it an octahedral
arrangement of electron pairs and a square planar geometry.

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

4.8 The Lewis structure is:

O
H
H C C O H
H

H O

H C AB4 tetrahedral C AB3 trigonal planar

H

O H AB2E2 bent

4.9 SiCl4, CI4, and CdCl42- would all be tetrahedral.

4.10 To predict the bond angles for the molecules, you would have to draw the Lewis structure and determine the
geometry using the VSEPR model. From the geometry, you can predict the bond angles.

(a) BeCl2: AB2 type, 180 (linear).

(b) BCl3: AB3 type, 120 (trigonal planar).

(c) CCl4: AB4 type, 109.5 (tetrahedral).

(d) Hg2Cl2: Each mercury atom is of the AB2 type. The entire molecule is linear, 180 bond angles.

(e) SnCl2: AB2E type, roughly 120 (bent).

(f) H2O2: The atom arrangement is HOOH. Each oxygen atom is of the AB 2E2 type and the HOO
angles will be roughly 109.5.
(g) SnH4: AB4 type, 109.5 (tetrahedral).

4.11 Only ICl2 and CdBr2 are linear. The rest are bent.

4.12 Only (c) will not be tetrahedral. All the others have AB4type Lewis structures and will therefore be
tetrahedral. For SF4 the Lewis structure is of the AB4E type which gives rise to a distorted tetrahedral
geometry (Table 4.2 of the text).

4.13 Geometry: bent; hybridization: sp3.

4.14 All four molecules have two bonds and two lone pairs (AB2E2) and therefore the bond angles are not linear.
Since electronegativity decreases going down a column (group) in the periodic table, the electronegativity
differences between hydrogen and the other Group 6 element will increase in the order Te < Se < S < O. The
dipole moments will increase in the same order. Would this conclusion be as easy if the elements were in
different groups?

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4.15 The electronegativity of the halogens decreases from F to I. Thus, the polarity of the HX bond (where X
denotes a halogen atom) also decreases from HF to HI. This difference in electronegativity accounts for the
decrease in dipole moment.

4.16 OCS is a linear molecule. Both S and O are more electronegative than C, so that the bond dipole moments of
the C=O and C=S bonds are nonzero and point towards the carbon atom. However, S is less electronegative
than O, so that the bond dipole moment of the C=O bond is larger in magnitude than that for the C=S bond,
resulting in an overall dipole moment that points from the O to the S atom.

BeCl2 is a linear molecule. Because Cl is more electronegative than Be, the Be-Cl bond is polar with a bond
dipole moment pointing towards the Be. However, the molecule is symmetric so that the two Be-Cl bond
dipoles will cancel to give a zero overall dipole moment.

OCl2 is a bent molecule with a structure similar to H2O. O is more electronegative than Cl, so that the O-Cl
bond is polar with a bond dipole pointing from O to Cl. Because the molecule is bent, the two bond dipole
moments do not cancel and there is a nonzero net molecular dipole moment pointing along the bisector of the
Cl–O–Cl angle from the O end of the molecule to the Cl end.

BCl3 has a trigonal planar geometry. Because Cl is more electronegative than B, the B-Cl bond is polar with a
bond dipole moment pointing towards the B. However, the molecule is symmetric so that the three B-Cl bond
dipoles will cancel to give a zero overall molecular dipole moment.

PCl3 has a trigonal pyramidal geometry with a structure similar to NH3. Cl is more electronegative than P, so
that the P–Cl bond is polar with a bond dipole pointing from Cl to P. There is also a dipole pointing from the
lone pair at the top of the PCl3 pyramid to the P. These four dipoles are symmetrically oriented, but they are
not all of the same magnitude, so they will not cancel and there will be nonzero net molecular dipole moment
pointing. The direction of this molecular dipole moment depends upon the relative magnitudes of the P–Cl
and P–(lone pair) dipoles.

SF6 has an octahedral geometry. Because F is more electronegative than S, the S–F bond is polar with a bond
dipole moment pointing towards the S. However, the molecule is symmetric so that the six S–F bond dipoles
will cancel to give a zero overall molecular dipole moment.

SF4 has a see-saw geometry. F is more electronegative than S, so that the S–F bond is polar with a bond dipole
pointing from F to S. There is also a dipole moment pointing from the lone pair on the S atom to the S atom.
Because the molecule has a see-saw shape, these five bond dipole moments are symmetrically oriented, but do
not cancel because the S–(lone pair) dipole moment will be of a different magnitude than the S–F bond dipole
moment, so the molecule has a nonzero net molecular dipole moment

So the molecules with nonzero dipole moments are OCS, OCl2, PCl3 and SF4

4.17 CO2  CBr4 (  0 for both) < H2S < NH3 < H2O < HF

4.18 While CS2 is non-polar, OCS is polar because oxygen is more electronegative than carbon.

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4.19 Dot structure Label Shape Bond dipole Resultant dipole moment

O
H H
AB2E2 bent >0

P
Cl Cl
Cl
AB3E trigonal >0
pyramidal

F F
Xe
F F
AB4E2 square planar 0

Cl
Cl
Cl P
Cl
Cl
AB5 trigonal bipyramid 0

F
F F
S
F F
F
AB6 octahedral 0

Why do the bond dipoles add to zero in PCl5?

F
C
Cl F
Cl
4.20

4.21
 +
C O
This is the only reasonable Lewis structure for CO. The electronegativity difference suggests that electron
density should concentrate on the O atom, but assigning formal charges places a negative charge on the C
atom. Therefore, we expect CO to have a small dipole moment. A resonance structure with a double bond

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

and formal charges of zero for both carbon and oxygen is considered less stable because carbon does not have
an octet.

4.22 For the point charge model, the dipole moment is equal to the size of the charge times the distance between
the charges (Equation 4.1). Hence, the charge is equal to the dipole moment divided by the distance between
the charges. For this problem we also have to know that 1 Debye equals 3.336 x 10 -30 C m and that a pm
equals 10-12 m.

   x 30
  20
q    12  x
r    

Which is equal to 44% the charge of an electron. So, of the two bonding electrons, 22% stays on the fluorine
giving the fluorine atom a negative charge, 22% is missing from the hydrogen, giving it a positive charge.

4.23 Molecule (b) will have a higher dipole moment. In molecule (a), the trans arrangement cancels the bond
dipoles and the molecule is nonpolar.

4.24 Strategy: Keep in mind that the dipole moment of a molecule depends on both the difference in
electronegativities of the elements present and its geometry. A molecule can have polar bonds (if the bonded
atoms have different electronegativities), but it may not possess a dipole moment if it has a highly symmetrical
geometry.

Solution: Each vertex of the hexagonal structure of benzene represents the location of a C atom. Around
the ring, there is no difference in electronegativity between C atoms, so the only bonds we need to consider
are the polar CCl bonds.
The molecules shown in (b) and (d) are nonpolar. Due to the high symmetry of the molecules and the equal
magnitude of the bond moments, the bond moments in each molecule cancel one another. The resultant
dipole moment will be zero. For the molecules shown in (a) and (c), the bond moments do not cancel and
there will be net dipole moments. The dipole moment of the molecule in (a) is larger than that in (c), because
in (a) all the bond moments point in the same relative direction, reinforcing each other (see structure below).
Therefore, the order of increasing dipole moments is:
(b)  (d) < (c) < (a).

(a)

4.25 AsH3 has the Lewis structure shown below. There are three bond pairs and one lone pair. The four electron
pairs have a tetrahedral arrangement, and the molecular geometry is trigonal pyramidal (AB 3E) like ammonia
(See Table 4.2). The As (arsenic) atom is in an sp3 hybridization state.

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H As H

Three of the sp3 hybrid orbitals form bonds to the hydrogen atoms by overlapping with the hydrogen 1s
orbitals. The fourth sp3 hybrid orbital holds the lone pair.

4.26 Strategy: The steps for determining the hybridization of the central atom in a molecule are:
draw the Lewis use VSEPR to determine the use Table 4.4 of
Structure of the electron pair arrangement the text to determine
molecule surrounding the central the hybridization
atom (Table 4.1 of the text) of the central atom
Solution:
(a) Write the Lewis structure of the molecule.
H
H Si H
H
Count the number of electron pairs around the central atom. Since there are four electron pairs around Si,
the electron arrangement that minimizes electron-pair repulsion is tetrahedral.

We conclude that Si is sp3 hybridized because it has the electron arrangement of four sp3 hybrid
orbitals.

(b) Write the Lewis structure of the molecule.

H H
H Si Si H
H H
Count the number of electron pairs around the “central atoms”. Since there are four electron pairs around
each Si, the electron arrangement that minimizes electron-pair repulsion for each Si is tetrahedral.
We conclude that each Si is sp3 hybridized because it has the electron arrangement of four sp3 hybrid
orbitals.

4.27 The Lewis structures of AlCl3 and AlCl4 are shown below. By the reasoning of the two Problems above, the
hybridization changes from sp2 to sp3.

Cl

Cl Al Cl Cl Al Cl

Cl Cl

What are the geometries of these molecules?

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4.28 Draw the Lewis structures. Before the reaction, boron is sp2 hybridized (trigonal planar electron arrangement)
in BF3 and the nitrogen is sp3 hybridized (tetrahedral electron arrangement) in NH3. After the reaction, boron
and nitrogen are both sp3 hybridized (tetrahedral electron arrangement).

4.29 The xenon is surrounding by four single bonds and two lone pairs (AB 4E2) and hence has sp3d2 hybridization.

4.30 (a) NH3 is an AB3E type molecule just as AsH3 in Problem 4.25. Referring to Table 4.4 of the text, the
nitrogen is sp3 hybridized.

(b) N2H4 has two equivalent nitrogen atoms. Centering attention on just one nitrogen atom shows that it is
an AB3E molecule, so the nitrogen atoms are sp3 hybridized. From structural considerations, how can
N2H4 be considered to be a derivative of NH3?

(c) The nitrate anion NO3 is isoelectronic and isostructural with the carbonate anion CO32. There are three
resonance structures, and the ion is of type AB3; thus, the nitrogen is sp2 hybridized.

4.31 (a) Each carbon has four bond pairs and no lone pairs and therefore has a tetrahedral electron pair
arrangement. This implies sp3 hybrid orbitals.
H H

H C C H

H H

(b) The left-most carbon is tetrahedral and therefore has sp3 hybrid orbitals. The two carbon atoms
connected by the double bond are trigonal planar with sp2 hybrid orbitals.
H H H

H C C C H

(c) Carbons 1 and 4 have sp3 hybrid orbitals. Carbons 2 and 3 have sp hybrid orbitals.
H H

H C1 C2 C3 C4 OH

H H

(d) The left-most carbon is tetrahedral (sp3 hybrid orbitals). The carbon connected to oxygen is trigonal
planar (why?) and has sp2 hybrid orbitals.
H H

H C C O

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

(e) The left-most carbon is tetrahedral (sp3 hybrid orbitals). The other carbon is trigonal planar with sp2
hybridized orbitals.
H O

H C C O H

4.32 (a) sp (b) sp (c) sp

4.33 Strategy: The steps for determining the hybridization of the central atom in a molecule are:
draw the Lewis use VSEPR to determine the use Table 4.4 of
Structure of the electron pair arrangement the text to determine
molecule surrounding the central the hybridization state
atom (Table 4.1 of the text) of the central atom

Solution:
Write the Lewis structure of the molecule. Several resonance forms with formal charges are shown.
         
N N N N N N N N N

Count the number of electron pairs around the central atom. Since there are two electron pairs around N, the
electron arrangement that minimizes electron-pair repulsion is linear (AB2). Remember, for VSEPR
purposes a multiple bond counts the same as a single bond.
We conclude that N is sp hybridized because it has the electron arrangement of two sp hybrid orbitals.

4.34 The Lewis structure is shown below. The two end carbons are trigonal planar and therefore use sp2 hybrid
orbitals. The central carbon is linear and must use sp hybrid orbitals.
H H

H C C C H

A Lewis drawing does not necessarily show actual molecular geometry. Notice that the two CH 2 groups at
the ends of the molecule must be perpendicular. This is because the two double bonds must use different 2p
orbitals on the middle carbon, and these two 2p orbitals are perpendicular. The overlap of the 2p orbitals on
each carbon is shown below.

C C C

Is the allene molecule polar?

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4.35 Strategy: The steps for determining the hybridization of the central atom in a molecule are:
draw the Lewis use VSEPR to determine the use Table 4.4 of
Structure of the electron pair arrangement the text to determine
molecule surrounding the central the hybridization state
atom (Table 4.1 of the text) of the central atom
Solution:
Write the Lewis structure of the molecule.

F
F P F
F
F

Count the number of electron pairs around the central atom. Since there are five electron pairs around P, the
electron arrangement that minimizes electron-pair repulsion is trigonal bipyramidal (AB5).

We conclude that P is sp3d hybridized because it has the electron arrangement of five sp3d hybrid orbitals.

4.36 (a) 4  bonds and 0  bonds.

(b) 5  bonds and 1  bonds.
(c) 10  bonds and 3  bonds.

4.37 A single bond is usually a sigma bond, a double bond is usually a sigma bond and a pi bond, and a triple bond
is always a sigma bond and two pi bonds. Therefore, there are nine pi bonds and nine sigma bonds in the
molecule.

4.38
CH3CH2CH2CH2CH2CH3

CH3 CH3
CH3CHCH2CH2CH3 CH3CH2CHCH2CH3

CH3 CH3
CH3CCH2CH3 CH3CHCHCH3
CH3 CH3

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

4.39 There are 14 structural isomers for C5H11OH. When trying to determine all of the structural isomers given a
formula try to be as systematic as possible.

OH OH OH

CH2CH2CH2CH2CH3 CH3CHCH2CH2CH3 CH3CHCCH2CH3

OH OH OH OH

CH2CHCH2CH3 CH3CCH2CH3 CH3CHCHCH3 CH3CHCH2CH2

CH3 CH3 CH3 CH3

CH3

CH3CCH2OH

CH3

CH3 CH3
H3C O CH2CH2CH2CH3 H3C O CHCH2CH3 H3C O CH2CHCH3

CH3 CH3
H3C O CCH3 H3CH2C O CH2CH2CH3 H3CH2C O CHCH3
CH3

4.40
Cl Cl H Cl H Cl
C C C
H C C H H C C Cl H C C H
H H H H H Cl

The first and second, and first and third are structural isomers. The second and third are geometric isomers.

4.41

OH OH

CH2CH2CH3 CH3CHCH3 H3C O CH2CH3

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4.42 The nitrate ion has a trigonal planar geometry. The 2p z orbitals on the oxygen and nitrogen atoms overlap
producing a molecular orbital that is above and below all three N-O bonds. The molecular orbital can be
written as a linear combination of the 2pz orbitals. From the symmetry of the molecule, we know that the
coefficient for the oxygen atomic orbitals are the same.

4.43 Ozone has a total of 18 valence electrons and consists of three atoms in a bent geometry. NO2 also consists
of three atoms in a bent geometry, but has one less valence electron. Hence, NO2 should have very
similar molecular orbitals with the highest energy occupied orbital (  Znonbonding ) being only half filled. Because
the only difference in the occupation of the orbitals is this nonbonding orbital, both ozone and NO 2 have three
bonding pairs of electrons spread over two bonds yielding bond orders of 1.5 and two resonance structures.
The bonding in ozone is discussed in Section 4.5 staring on page 257 of the text.

4.44 NO2– has a bent geometry (like ozone, which which it is isoelectronic) and has two electrons in the
lowest energy  orbital. This  orbital is formed from the 2pz orbitals of the nitrogen and oxygen atoms and
is above and below both nitrogen-oxygen bonds. NO2+ has a linear geometry (like CO2, with which it is
isoelectronic) and has four electrons in  orbitals. The lowest energy  orbital of NO2+ is similar to that of
NO2-, in that it could be composed of the 2pz orbitals of the nitrogen and oxygen atoms and is above and
below both nitrogen-oxygen bonds. The lowest energy  orbital of NO2+ could also be composed of the 2py
orbitals of the nitrogen and oxygen atoms. Hence, NO2+ has two degenerate  orbitals. Notice that because of
the symmetry of both NO2- and NO2+, the coefficients for the oxygen atomic orbitals are the same.

 z  c1O ,2 p  c2 N ,2 p  c1O

1 z z 2 ,2 pz

 y  c1O ,2 p  c2 N ,2 p  c1O

1 y y 2 ,2 p y

4.45 If the two rings happen to be perpendicular in biphenyl, the  molecular orbitals are less delocalized. In
naphthalene the  molecular orbital is always delocalized over the entire molecule. What do you think is the
most stable structure for biphenyl: both rings in the same plane or both rings perpendicular?

4.46 The ion contains 24 valence electrons. Of these, six are involved in three sigma bonds between the nitrogen
and oxygen atoms. The hybridization of the nitrogen atom is sp2. There are 16 non-bonding electrons on the
oxygen atoms. The remaining two electrons are in a delocalized  molecular orbital which results from the
overlap of the pz orbital of nitrogen and the pz orbitals of the three oxygen atoms.

4.47 As discussed in the text (see Table 3.4), the single bond in B2 is a  bond (the electrons are in a  bonding
molecular orbital) and the double bond in C2 is made up of two  bonds (the electrons are in the  bonding
molecular orbitals).

4.48 ICl has a dipole moment and Br2 does not. The dipole moment increases the intermolecular attractions
between ICl molecules and causes that substance to have a higher melting point than bromine.

4.49 (a) Benzene (C6H6) molecules are nonpolar. Only dispersion forces will be present.

(b) Chloroform (CH3Cl) molecules are polar (why?). Dispersion and dipole-dipole forces will be present.

(c) Phosphorus trifluoride (PF3) molecules are polar. Dispersion and dipole-dipole forces will be present.
(d) Sodium chloride (NaCl) is an ionic compound. Ion-ion (and dispersion) forces will be present.
(e) Carbon disulfide (CS2) molecules are nonpolar. Only dispersion forces will be present.

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4.50 CO2 < CH3Br < CH3OH < RbF

CO2 is a nonpolar molecular compound. The only intermolecular force present is a relatively weak dispersion
force (small molar mass). CO2 will have the lowest boiling point.

CH3Br is a polar molecule. Dispersion forces (present in all matter) and dipoledipole forces will be present.
This compound has the next highest boiling point.
CH3OH is polar and can form hydrogen bonds, which are especially strong dipole-dipole attractions.
Dispersion forces and hydrogen bonding are present to give this substance the next highest boiling point.
RbF is an ionic compound (Why?). Ionion attractions are much stronger than any intermolecular force. RbF
has the highest boiling point.

4.51 (a) Cl2: it has more electrons the O2 (both are nonpolar) and therefore has stronger dispersion forces.

(b) SO2: it is polar (most important) and also has more electrons than CO 2 (nonpolar). More electrons
imply stronger dispersion forces.
(c) HF: although HI has more electrons and should therefore exert stronger dispersion forces, HF is capable
of hydrogen bonding and HI is not. Hydrogen bonding is the stronger attractive force.

4.52 (a) Ne: it has fewer electrons and therefore weaker dispersion forces.
(b) CO2: it has fewer electrons (both molecules nonpolar) and therefore weaker dispersion forces.

(c) CH4: it has fewer electrons (both molecules nonpolar) and therefore weaker dispersion forces.
(d) F2: is a nonpolar molecular compound with just dispersion forces. The ion-ion attractions in LiF are
much stronger than the dispersion forces between F2 molecules.

(e) PH3: NH3 can form hydrogen bonds and PH3 cannot.

4.53 (a) Boiling liquid ammonia requires breaking hydrogen bonds between molecules. Dipoledipole and
dispersion forces must also be overcome.
(b) P4 is a nonpolar molecule, so the only intermolecular forces are of the dispersion type.
(c) CsI is an ionic solid. To dissolve in any solvent ionion interparticle forces must be overcome. To
dissolve something in HF, some of the hydrogen bonds, dipole-dipole and dispersion forces between HF
molecules must also be overcome.

4.54 LiF, ionic bonding and dispersion forces; BeF2, ionic bonding and dispersion forces; BF3, dispersion forces;
CF4, dispersion forces; NF3, dipole-dipole interaction and dispersion forces; OF2, dipole-dipole interaction
and dispersion forces; F2, dispersion forces.

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4.55 The potential energy due to the dipole-induced dipole interaction between a water molecule and an argon
atom can be calculated using Equation 4.9 on page 268 of the text. By slightly modifying this equation it is a
little easier to follow the calculation.

 2  2 1
V  
4  r 4 0 4 0 r 6
2 6
0

The quantity  is the polarizability of the argon atom and its value is given in Table 4.5. The dipole moment
of water is 1.87 D (Table 4.3).

2
  3.336  10 ? 0 C m  
(1.87 D)  
V 
  30 3
   1D  1
  23
 1.39  1023 J
1 4 (8.854  10 C N m ) (6.0  10 10 m) 6
? 2 2 ? ?

4.56 We can calculate the potential energy of the interaction between two polar molecules that are antialigned
using equation 4.5 on page 266. The dipole moment of ammonia (NH 3) is 1.46 D (given in Table 4.3).

A  B
V 
4 0 r 3

2
  3.336  10? 0 C m  
(1.46 D)  
  1D 
V   3.3  10? 1 N m  3.3  1021 J
4 (8.854  10 C N m )(4.0  10 m)
? 2 2 ? ? 10 3

4.57 The potential energy due to the interactions of two identical atoms or nonpolar molecules is given by Equation
4.10 in the text.

3  2 I1
V –
4 (4 0 ) 2 r 6

Plugging in the polarizability () from Table 4.5, and first ionization energy (I1) per atom (not per mole)
modified from Table 2.2, for argon, we calculate that the potential energy for the interaction between two
argon atoms separated by 5.00 Å to be
3  
30 3 2 18
 
V ? 4.15  10-22 J
 
10 6
4 

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

4.58

The potential for the xenon has a more negative potential well indicating that xenon-xenon intermolecular
interactions are stronger than argon-argon interactions and that xenon should have a higher boiling point. The
xenon potential become positive at a large r, indicating that xenon atoms are larger than argon atoms.

4.59 Strategy: The sequence of steps in determining molecular geometry is as follows:

draw Lewis 
 find arrangement of 
 find arrangement 
 determine geometry
structure electrons pairs of bonding pairs based on bonding pairs

Solution:
Write the Lewis structure of the molecule.

Br Hg Br

Count the number of electron pairs around the central atom. There are two electron pairs around Hg.

Since there are two electron pairs around Hg, the electron-pair arrangement that minimizes electron-pair
repulsion is linear.
In addition, since there are no lone pairs around the central atom, the geometry is also linear (AB2).

You could establish the geometry of HgBr2 by measuring its dipole moment. If mercury(II) bromide were
bent, it would have a measurable dipole moment. Experimentally, it has no dipole moment and therefore must
be linear.

4.60 (a) The Lewis structure is:

F B F

The shape will be trigonal planar (AB3)

(b) The Lewis structure is:

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

-
O Cl O

O
The molecule will be a trigonal pyramid (nonplanar).
(c) The Lewis structure is:

O
H H

The dipole moment is bisects the hydrogen-oxygen-hydrogen bond and goes from the partial negative
oxygen to the more positive hydrogen.

(d) The Lewis structure is:

O

F F
The molecule is bent and therefore polar.

(e) The Lewis structure is:

O O

The nitrogen atom is of the AB2E type, but there is only one unshared electron rather than the usual pair.
As a result, the repulsion will not be as great and the ONO angle will be greater than 120 expected
for AB2E geometry. Experiment shows the angle to be around 135.

Which of the species in this problem has resonance structures?

4.61 To predict the bond angles for the molecules, you would have to draw the Lewis structure and determine
the geometry using the VSEPR model. From the geometry, you can predict the bond angles.

(a) BeCl2: AB2 type, 180 (linear).

(b) BCl3: AB3 type, 120 (trigonal planar).

(c) CCl4: AB4 type, 109.5 (tetrahedral).

(d) CH3Cl: AB4 type, 109.5 (tetrahedral with a possible slight distortion resulting from the different
sizes of the chlorine and hydrogen atoms).
(e) Hg2Cl2: Each mercury atom is of the AB2 type. The entire molecule is linear, 180 bond angles.

(f) SnCl2: AB2E type, roughly 120 (bent).

(g) H2O2: The atom arrangement is HOOH. Each oxygen atom is of the AB 2E2 type and the HOO
angles will be roughly 109.5.

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

(h) SnH4: AB4 type, 109.5 (tetrahedral).

4.62 AsF5 is an AB5 type molecule, so the geometry is trigonal bipyramidal. We conclude that As is sp3d
hybridized because it has the electron arrangement of five sp3d hybrid orbitals.

4.63 In 1,2-dichloroethane, the two C atoms are joined by a sigma bond. Rotation about a sigma bond does not
destroy the bond, and the bond is therefore free (or relatively free) to rotate. Thus, all angles are permitted
and the molecule is nonpolar because the CCl bond moments cancel each other because of the averaging
effect brought about by rotation. In cis-dichloroethylene the two CCl bonds are locked in position. The
 bond between the C atoms prevents rotation (in order to rotate, the  bond must be broken, using an energy
source such as light or heat). Therefore, there is no rotation about the CC in cis-dichloroethylene, and the
molecule is polar.

4.64 Consider the overlap of the 2p orbitals on each carbon atom.

C C C

The geometric planes containing the CHCl groups at each end of the molecule are perpendicular. This is
because the two carbon-carbon double bonds must use different 2p orbitals on the middle carbon, and these
two 2p orbitals are perpendicular. This means that the two chlorine atoms can be considered to be on one side
of the molecule and the two hydrogen atoms on the other. The molecule has a dipole moment. Draw the end-
on view if you aren't convinced.

4.65 O3, CO, CO2, NO2, N2O, CH4, and CFCl3 are greenhouse gases.

4.66 (a) The Lewis structure is:

O
O S O
The geometry is trigonal planar; the molecule is nonpolar.

(b) The Lewis structure is:

F

F P F
The molecule has trigonal pyramidal geometry. It is polar.

(c) The Lewis structure is:

H

F Si F

The molecule will be tetrahedral (AB4). Both fluorine and hydrogen are more electronegative than
silicon, but fluorine is the most electronegative element, so the molecule will be polar (fluorine side
negative).

(d) The Lewis structure is:

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

H 

H Si H
The ion has a trigonal pyramidal geometry (AB3E).

(e) The Lewis structure is:

H

Br C Br

The molecule will be tetrahedral (AB4) but still polar. The negative end of the dipole moment will be on
the side with the two bromine atoms; the positive end will be on the hydrogen side.

4.67 The Lewis structure is shown below.

2
Cl

Cl Be Cl

Cl
The molecule is of the AB4 type and should therefore be tetrahedral. The hybridization of the Be atom
should be sp3.

-
Cl O N O
+
4.68
The nitrogen is sp2 and has a trigonal planar geometry resulting in O-N-O bond angles of 120˚. The oxygen is
sp3 and has a bent geometry resulting in a Cl-O-N bond angle of less than 109.5˚.

4.69 As the molecule is heated, its internal motion increases. As the molecule twists about the carbon-carbon
double bond the chlorine atoms spend less time in the same plane, reducing the molecule’s dipole moment. If
the molecule is heated to a high enough temperature eventually there will be complete rotation about the
carbon-carbon double bond.

4.70 The Lewis structures and VSEPR geometries of these species are shown below. The three nonbonding pairs
of electrons on each fluorine atom have been omitted for simplicity.
F
F F F F
 
F Xe F Xe

Sb
F F F F F
F F
AB3E2 AB5E AB6
T-shapedSquare Pyramidal Octahedral

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

4.71 The sulfur in SO2 has three regions of electron density and hence trigonal planar electron geometry. Because
lone pairs of electrons typically take more space, we would expect a bond angle of less than 120˚. But,
because both sulfurtooxygen bonds are double bonds, which occupy more space than single bonds, the
angle is close to 120.

4.72 Only ICl2 and CdBr2 will be linear. The rest are bent.

4.73 VSEPR theory enables us to determine a molecule’s geometry from the number of regions of electron density
around the center atom. Hybridization enables us to understand how the atomic orbitals are changed to
accommodate these geometries.

4.74 Since nitrogen is a second row element, it cannot exceed an octet of electrons. Since there are no lone pairs
on the central nitrogen, the molecule must be linear and sp hybrid orbitals must be used.

+ 2  +  2 +
N N N N N N N N N

The 2py orbital on the central nitrogen atom overlaps with the 2py on the terminal nitrogen atoms, and the 2pz
orbital on the central nitrogen overlaps with the 2pz orbitals on the terminal nitrogen atoms to form
delocalized molecular orbitals.

4.75 1 D  3.336  1030 Cm

electronic charge (e)  1.6022  1019 C

3.336  1030 C  m
1.92 D 
 1D
 100%   100%  43.6% ionic character
ed 19
(1.6022  10 C)  (91.7  1012 m)

4.76
F H F F F H
C C C C C C
F H H H H F
polar polar nonpolar

4.77 (a)

Cl Cl Cl
Al Al
Cl Cl Cl

(b) The hybridization of Al in AlCl3 is sp2. The molecule is trigonal planar. The hybridization of Al in
Al2Cl6 is sp3.

(c) The geometry about each Al atom is tetrahedral.

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

Cl Cl Cl
Al Al
Cl Cl Cl
(d) The molecules are nonpolar; they do not possess a dipole moment.

4.78
P
P P P

The four P atoms occupy the corners of a tetrahedron. Each phosphorus atom is sp3 hybridized.

The P2 molecule has a triple bond, which is composed of one sigma bond and two pi bonds. The pi bonds are
formed by sideways overlap of 3p orbitals. Because the atomic radius of P is larger than that of N, the overlap is
not as extensive as that in the N2 molecule. Consequently, the P2 molecule is much less stable than N2 and also
less stable than P4, which contains only sigma bonds.

4.79 According to valence bond theory, a pi bond is formed through the side-to-side overlap of a pair of p orbitals.
As atomic size increases, the distance between atoms is too large for p orbitals to overlap effectively in a side-
to-side fashion. If two orbitals overlap poorly, that is, they share very little space in common, then the
resulting bond will be very weak. This situation applies in the case of pi bonds between silicon atoms as well
as between any other elements not found in the second period. It is usually far more energetically favorable
for silicon, or any other heavy element, to form two single (sigma) bonds to two other atoms than to form a
double bond (sigma  pi) to only one other atom.

4.80 (a) The potential energy due to the interactions of two identical atoms or nonpolar molecules is given by

3  2 I1
V – .
4 (4 0 ) 2 r 6

Plugging in the polarizability (), from Table 4.5, and first ionization energy (I1) per atom (not per mole)
modified from Table 2.2, for argon, we calculate that the potential energy for the interaction between
two argon atoms separated by 5.00 Å to be

3  
30 3 2 18
 
V ? 4.15  10-22 J
 
10 6
4 

(b) For nonidentical atoms or molecules A and B, Equation 4.10 becomes

3 I1,A I1,B  A B
V Š
2 I1,A  I1,B (4 0 )2 r 6

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

Plugging in the polarizabilities (), from Table 4.5, and first ionization energies (I1) per atom (not per mole)
modified from Table 2.2, for argon and neon, we calculate that the potential energy for the interaction
between these two atoms separated by 5.00 Å to be

        
3 
18 18 30 30
    3
 3

V ?    5.70  10-23 J
4   18
  18
     10

6

 

4.81 The Lewis structure is:

O
H C* CH3
*
N C
*C C*
O N H
HO CH2
O
CH HC
HC CH

*N H

N#

N
*
The carbon atoms and nitrogen atoms marked with an asterisk (C and N) are sp2 hybridized; unmarked
carbon atoms and nitrogen atoms are sp3 hybridized; and the nitrogen atom marked with (#) is sp hybridized.

4.82 The carbons are in sp2 hybridization states. The nitrogens are in the sp3 hybridization state, except for the
ring nitrogen double-bonded to a carbon that is sp2 hybridized. The oxygen atom is sp2 hybridized.

4.83 C has no d orbitals but Si does (3d). Thus, H2O molecules can add to Si in hydrolysis (valence-shell
expansion).

4.84 Butane should have the highest boiling point because the butane molecules have larger surface resulting in
more intermolecular interactions.

4.85 CCl4 can be represented by:

Cl
C
Cl 
Cl
Cl

Let  be a CCl bond moment. Thus,

  3 cos 

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

1
cos     70.5
3

Tetrahedral angle  180  70.5  109.5

4.86 SiO2 has an extensive three-dimensional structure. CO2 exists as discrete molecules. It will take much more
energy to break the strong network covalent bonds of SiO2; therefore, SiO2 has a much higher boiling point
than CO2.

4.87 (a) Two Lewis resonance forms are shown below. Formal charges different than zero are indicated.

F F
 
O N O O N O
 

(b) There are no lone pairs on the nitrogen atom; it should have a trigonal planar electron pair arrangement
and therefore use sp2 hybrid orbitals.

(c) The bonding consists of sigma bonds joining the nitrogen atom to the fluorine and oxygen atoms. In
addition there is a pi molecular orbital delocalized over the N and O atoms. Is nitryl fluoride
isoelectronic with the carbonate ion?

4.88 (a)
Strategy: The steps for determining the hybridization of the central atom in a molecule are:
draw the Lewis use VSEPR to determine the use Table 4.4 in
Structure of the electron pair arrangement the text to determine
molecule surrounding the central the hybridization state
atom (Table 4.1 in the text) of the central atom

Solution:
The geometry around each nitrogen is identical. To complete an octet of electrons around N, you must add a
lone pair of electrons. Count the number of electron pairs around N. There are three electron pairs around
each N.

Since there are three electron pairs around N, the electron-pair arrangement that minimizes electron-pair
repulsion is trigonal planar.

We conclude that each N is sp2 hybridized because it has the electron arrangement of three sp2 hybrid
orbitals.

(b) Strategy: Keep in mind that the dipole moment of a molecule depends on both the difference in
electronegativities of the elements present and its geometry. A molecule can have polar bonds (if the bonded
atoms have different electronegativities), but it may not possess a dipole moment if it has a highly symmetrical
geometry.

Solution: An NF bond is polar because F is more electronegative than N. The structure on the right has a
dipole moment because the two NF bond moments do not cancel each other out and so the molecule has a
net dipole moment. On the other hand, the two NF bond moments in the left-hand structure cancel. The sum
or resultant dipole moment will be zero.

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

4.89 Benzene is stabilized by delocalized molecular orbitals. The CC bonds are equivalent, rather than
alternating single and double bonds. The additional stabilization makes the bonds in benzene much less
reactive chemically than isolated double bonds such as those in ethylene.

4.90 Each of the oxygen atoms in O2 is sp2 hybridized. Two of the hybrid orbitals on each oxygen contain lone
pairs of electrons. The remaining hybrid orbital on each oxygen overlaps with each other forming a  bond.
The two unhybridized 2p orbitals on each oxygen overlap forming a  bond. If we think about the bonding of
O2 in terms of unhybridized orbitals, we can imagine that the  and  bonds are formed by the overlap of 2p
orbitals and that one lone pair on each atom remains in a 2s orbital and the other in a 2p orbital.

4.91 (a) Although the O atoms are sp3 hybridized, they are locked in a planar structure by the benzene rings. The
molecule is symmetrical and therefore does not possess a dipole moment.

(b) 20  bonds and 6  bonds.

4.92 We can calculate the potential energy of the interaction between two polar molecules that are antialigned
using equation 4.5 on page 266:

 AB
V 
4 0 r 3

2
  3.336  10? 0 C m  
 (1.87 D)  
  1D 
V   1.3  10? 0 N m  1.3  10 ? 0 J
4 (8.854  10? 2 C2 N ? m ? )(3.0  1010 m)3

We can calculate the strength of the interaction between two ions using equation 4.2 on page 264:

qA qB
V
4 0 r

For this problem we are trying to determine r. So, we can easily solve for r in the above equation:

q q
r A B 
  19
   19
   8

4 0V   ? 2 2 ? ?
  20


4.93
H
C C O
H
sp2 sp

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

H
 bonds C C O
H

 bonds C C O

4.94 The complete structure of progesterone is shown below.

CH3

H2 *C O
CH3
C
CH
H2C C
H2 CH3 CH2
C CH CH
C
H2C C CH
H2

C* *C CH2
*C C
O
H H2

The four carbons marked with an asterisk are sp2 hybridized. The remaining carbons are sp3 hybridized.

4.95 (a)
 +
C O
This is the only reasonable Lewis structure for CO. The electronegativity difference suggests that
electron density should concentrate on the O atom, but assigning formal charges places a negative charge
on the C atom. Therefore, we expect CO to have a small dipole moment.

(b) The Lewis structure shows a triple bond. The molecular orbital description gives a bond order of 3, just
like N2.

(c) Normally, we would expect the more electronegative atom to bond with the metal ion. In this case, however,
the small dipole moment suggests that the C atom may form a stronger bond with Fe2 than O. More
elaborate analysis of the orbitals involved shows that this is indeed the case.

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 CHAPTER 4: MOLECULAR STRUCTURE AND INTERACTION

82