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Molecular Structure

I. Valence Bond Theory


A. General
1. We will consider the covalent compounds formed by the interactions of nonmetals.
2. They interact by “sharing electrons” between them.
3. Two theories, the valence bond theory and the molecular orbital theory, have been
developed to analyze these interactions and rationalize some important properties of
covalent compounds.
B. Valence Bond: Orbital overlap and the covalent bond. The H2 molecule
1. Consider two hydrogen atoms forming an H2 molecule. Originally each H has an
electron in a spherically symmetric 1s orbital. Consider what happens as the two H
atoms approach one another.
Overlap region

HA 1sA1 HB 1sB1 H2
Lewis diagram H• •H H:H or H–H
2. When the two atoms get close enough, their electron clouds can interpenetrate one
another, that is, the orbitals can overlap so that there are common regions where both
1s wave functions are sizable.
a. When an electron enters this region of overlap, it will lose its identify and could just
as well move about nucleus A or B. In this way the two electrons are shared by
both nuclei.
b. This sharing results in a lowering of the energies of the electrons, because
1) the potential energies decrease because the electrons can be close to two nuclear
centers.
2) the kinetic energies of the electrons decrease because they can occupy larger
regions in space.
c. The energy lowering gives rise to a directional force of attraction between the two
atoms, called a covalent bond or an electron pair bond.
3. We can think of a covalent bond being formed by the overlap of two half-filled orbitals,
one on each atom. It is also possible to form a covalent bond by the overlap of a vacant
orbital on one atom with a filled orbital on another, such a covalent bond is called a

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coordinate covalent bond. In either case, the covalent bond involves two orbitals and
two electrons.
4. Since the two electrons in a bond can occupy the same orbital, their spins must be paired.
C. Consider two F atoms forming an F2 molecule.
1. The electron configuration of F is 1s22s22p5. The valence electrons are distributed as
↑↓ ↑↓ ↑↓ ↑
2s 2p

2. The two half-filled p orbitals can overlap to form a F–F bond.

F F F F

F F – –
F F or –F–F



3. In the F2 molecule, each F atom will have four electron pairs associated with it, one
shared pair and three other pair that are not shared.
4. The unshared pairs are called lone pairs.
D. Summary.
1. Consider only the valence electrons.
2. Molecule is held together by adjacent atoms sharing pairs of electrons, giving a series of
electron pair bonds. The shared electrons are said to be delocalized about the two atoms.
3. The sharing is accomplished by the overlap of an orbital on one atom and an orbital on an
adjacent atom (two half-filled or one vacant and a completely filled orbital). The greater
the overlap of the orbital, the stronger the bond. Since both electrons can occupy the
same orbital, their spins must be paired.
4. Those electrons not involved in bonding are localized on the individual atom as lone
pairs.
5. The bonding pattern is described by drawing Lewis diagrams (or electron-dot diagrams).

II. Lewis Diagrams—Show the arrangement of the valence electrons, in terms of lone pairs and
bonding pairs, about each atom in a molecule.
A. Multiple bonding.
1. Types of bond possible.
a. Single bond: atoms share one pair of electrons—utilizes one orbital from each atom.
b. Double bond: atoms share two pairs of electrons-- utilizes two orbitals from each atom.

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c. Triple bond: atoms share three pairs of electrons-- utilizes three orbitals from each
atom.
2. For the same atoms, triple bonds are the strongest and shortest while single bonds are
the weakest and give rise to the longest bond lengths. Example:
Bond Bond Strength Bond distance
Bond type __(kJ/mol)____ (pm)____
C−C single 347 154
C=C double 620 133
C≡C triple 812 120
3. Valence electrons not involved in bonding are localized on the individual atoms as
lone pairs.
4. In many compounds, the atoms utilize all of their valence s and p orbitals in bonding
and thus obey the octet rule.
a. Sum of lone pairs + bonding pairs = 8 (4 pairs).
b. For hydrogen, two electrons (1 pair).
5. Coordinate covalent bond = bond formed by the overlap of a filled orbital on one
atom and a vacant orbital on another atom.

+
H
H

H N + H+ H N H

H lone pair H coordinate covalent bond

6. There are a number of approaches to drawing Lewis diagrams. Two ways will be shown
on the following pages.
a. In one method one starts with the valence electrons placed about each atom and
consider how they can be combined to form sufficient single double and triple bonds
to give the final Lewis diagram of the molecule.
b. In the other method, all valence electrons are formed into pairs and then the pairs are
arranged as lone pair or bonding pairs about each atom in the molecule. This
method makes no distinction between covalent and coordinate covalent bonds.

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B. Some simple Lewis diagrams.
1. Neutral molecules—Nonmetal hydrides.
a. HF H F H F or H F

b. H2 O 2H O H O H H O
H
H-O-H H-O
H
c. NH3 3H N H N H H-N-H
H H

H H
d. CH4 4H C H C H H-C-H
H H

HH H H
e. C2 H6 6H 2 C H C C H H C C H
H H H H
Single
Bond
f. C2 H4 4H 2 C H C C H
H C C H
H H H H
Double
Bond

g. C2 H2 2H 2 C H C C H H C C H
Triple
Bond
2. Alternate approach
a. Consider C2H6 2C = 8e H H
6H = 6e | |
Total = 14e = 7 – H–C–C–H
| |
H H

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Consider C2H2 2C = 8e
2H = 2e H–C≡C–H
Total = 10e = 5–

b. Complex ions.
2-
SO4 S = 6e |O| 2-
4O = 24e |
2 – = 2e |O–S–O|
32e = 16 – |
|O|
+
NO2 N = 5e
2O = 12e [ O = N = O ]+
+ = -1e
16e = 8 –

3. Nonoctet compounds
a. Less than eight (electron deficient compounds)
BeCl2 Be = 2e
2Cl = 14e | Cl – Be – Cl |
16e = 8 –
BF3 B = 3e |F|
3F = 21e |
24e = 12 – |F–B–F|

Even though there are enough electrons so that the central atoms could satisfy its octet
through coordinate covalent bonding, these atoms are not electronegative enough to do this.
b. Expanded octets ( hypervalent compounds)
PF5 P = 5e |F|
5F = 35e F|
40e = 20 – |F–P
F|
|F|
BrF3 Br = 7e |F|
3F = 21e
28e = 14 – Br – F |

|F |

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SF6 S = 6e |F|
6F = 42e F|
48e = 24 – |F S F|
|F
|F|
Note that in drawing the Lewis diagram the central atom will have the extra bonds or
lone pairs, the atoms around the periphery obey the octet rule. The central atom will
be in the third or higher period in the Periodic Table.
c. Odd electron molecules. When there is an odd number of electrons, it is not possible
for each atom to have its octet. An example of such a molecule is NO, which has 11
electrons. The best Lewis diagram for the molecule is

N O

These compounds are better treated using Molecular Orbital theory.


C. Formal Charge (FC)
1. The Formal Charge is a parameter that is assigned to each atom in a molecule that
can help keep track of the types of bonds formed and aid in selecting the best of
several possible Lewis diagrams. It is not a charge in the usual sense.
2. Formal Charge (FC) = number of valence electron – number of electrons in lone pairs
– 1/2(number of electron in bonds)
3. Examples.
a. FC’s in SO42– The Lewis diagram of SO42– is
2–
O

O S O

FC(S) = 6 – 0 – 1/2(8) = +2 FC(O) = 6 – 6 –1/2(2) = –1


Note:
1) ∑FC’s = the charge on the formula. For SO42– ∑ = +2 + 4(–1) = –2
2) When an atom donates a pair of electrons in forming a coordinate covalent
bond, its formal charge will go up by one.
3) In general, the FC’s should be as low as possible (ideally zero) and the more
electronegative elements should not have positive FC’s.

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4) Many times Lewis diagrams are drawn so as the minimize Formal Charges. For
example, SO 2"
4 could be written as
|O| |O| 2-
|| |
|O—S—O| O=S=O
! || |
|O| |O|
With this diagram: FC(S) = 6 – ½(12) = 0; FC(O=) = 6 – 4- ½(4) = 0
FC(O-) = 6 – 6 – ½(2) = -1. Because of resonance, the O’s will have the same
Formal Charge of -1/2.
It should be emphasized that there is no experimental way to distinguish between
the two Lewis structures, they both give rise to the same properties.
b. Consider NO2+ _+

If the Lewis diagram is O=N=O ,


FC(N) = 5 – 1/2(8) = 1, FC(O) = 6 – 4 –1/2(4) = 0
If Lewis diagram is O=O=N ,
FC(N) = 5 – 4 –1/2(4) = –1 FC(O) = 6 – 0 –1/2(8) = +2 (middle)
FC(O) = 6 – 4 – 1/2(4) = 0 The – FC on N and the +2 FC on O is not reasonable.
c. Consider NO
If the Lewis diagram is •N=O|, FC(N)=5 – 3 – 1/2(4) = 0, FC(O)=6 – 4 – 1/2(4) = 0
If the Lewis diagram is |N=O•, FC(N)=5 – 4—1/2(4) = –1, FC(O)=6 –3 –1/2(4) = 1
The first Lewis diagram is more reasonable.
C. Resonance
1. Consider SO3 (24e = 12 – )
O

S
O O

a. This Lewis diagram shows one sulfur-oxygen double bond and two sulfur-oxygen
single bonds. On this basis one would predict one short, strong bond and two longer,
weaker bonds.
b. Experimentally it is known that the three sulfur-oxygen bonds are identical.
c. Note that equivalent Lewis diagrams could have been drawn with the double bond
written between the sulfur and each oxygen. The only acceptable picture is that
given by all three diagrams.

O O O

S S S
O O 7 O O O O
d. The molecule undergoes resonance. Each Lewis diagram is said to be a
contributing form to the resonance hybrid. Note that SO3 has a single dynamic
electronic structure; it requires three still pictures (Lewis diagrams) to describe it.
e. SO3 is more stable than expected from one sulfur-oxygen double bond and two
sulfur-oxygen single bonds. The molecule is said to be resonance stabilized.
d. Whenever you can draw more than one equivalent Lewis diagram, by shifting double
bonds, the substance exhibits resonance and all Lewis diagrams must be drawn and
connected by double headed arrows.
2. Other examples.
O O|
-
a. NO2 (18e = 9 – ) |N |N
O| O
b. CO2 (16e = 8 – ) [ O=C=O ↔ |O–C≡O| ↔ |O≡C–O| ]

D. Lewis Diagram Summary

1. Determine the number of valence electron pairs that are to be used including any changes
due to charges. You must use all of these pairs and only these pairs.
2. In substances with several different elements, the least electronegative element usually is
the central atom.
3. First, try to draw the diagram using the octet rule, single bonds and lone pairs. If this is
possible, then that is the Lewis diagram.
a. If you are one pair short, the substance has a double bond.
b. If you are two pairs short, the substance has a triple or two double bonds.
4. If there are electron pairs left over, they go as lone pairs around the central atom
(the central atom will have an "expanded octet").
5. Electron deficient compounds are found in some boron or metal containing compounds
when an octet can be obtained only if the boron or metal accepts electron pairs in forming
coordinate covalent bonds. Since these atoms are not electronegative enough to do this, the
central boron or metal will not have its octet.
6. Calculate the FC’s and make sure they are reasonable.

II. Shapes of molecules – Valence Shell Electron Pair Repulsion (VSEPR) Model.
A. Approach.
1. Draw Lewis diagram.

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2. Count the number of lone pairs (L) + atoms bonded(B) around each central atom.
At this point, it does not matter whether the atoms are bonded by single, double, or triple
bonds.
3. These groups will repel one another and arrange themselves about the central atom so as
to get as far away from one another as possible. The order of repulsion is:

lone pairs >> triple bonds > double bonds > single bonds.

4. If the sum of L+B about a central atom is equal to

a. 2, the arrangement is linear.

b. 3, the arrangement is trigonal planar.

120 '

All three sites are equivalent

c. 4, the arrangement is tetrahedral.

109'28''

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All four positions are equivalent.

d. 5, the arrangement is trigonal bipyramidal.

o
90
o
120

1) All five positions are not equivalent.


2) The three positions in the trigonal plane are the equatorial positions.
3) The two above and below the equatorial plane are the axial positions.

e. 6, the arrangement is octahedral.

o
90
90 o

All six positions are equivalent.

B. Examples.

1. B+L=2; Linear

O=C=O H-C≡C-H

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2. L+B = 3 F
a. B = 3, L = 0

120°
Example BF3
B TRIGONAL PLANAR or
PLANAR TRIANGULAR

F F

b. B = 2, L = 1

Example NO2–
(18 e- system) >120° V SHAPED or BENT

m N
p
12 3 .6
O O
115.4°

NO2
(17 e- system)

N
p m
11 9 .7
O O
134.3°

Note that one electron takes up less room than either a


bonded pair or a lone pair.

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3. L + B = 4; Tetrahedral.
a. B = 4, L = 0 CH4, SO 42-, NH 4+ 109' 28"

O
TETRAHEDRAL

H O H

C S
H N
O H
H O
H O H
H

b. B = 3, L = 1 NH3 SO32-

TRIGONAL
O PYRAMID

< 109'

N
H S
H O
H O
O
107'

c. B = 2, L = 2 H2O

V SHAPED
O or
BENT
H
H
104' 30"

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4. L + B = 5; Trigonal Bipyramid.

a. B = 5, L = 0 PF5 F
90' 158.0 pm
F
O F P
152.2 pm
120'
F

The F's are not equivalent. The two axial bonds are158 pm
and the three equatorial bonds are152 pm

F
b. B = 4, L = 1 SF4 86.6°
164.6 pm
F
S 101.6°
F

F 154.5 pm

c. B = 3, L =2 BrF3 F 86.2 °
181 pm
F
Br "T" SHAPED
172.2 pm

d. B = 2, L = 3 I3–

I –

LINEAR
I

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5. L + B = 6; Octahedral
a. B = 6, L = 0 SF 4 F 90 '

F F
OCTAHEDRAL
S 90 '

F F

b. B = 5, = 1 IF5 < 90 '


F

F F SQUARE
I 90 ' PYRAMID

F F

c. B = 4, L = 2 XeF4

F F
Xe 90 ' SQUARE
PLANAR
F F

C. Other Considerations.
1. Electronegativity differences.
a. Electron-electron repulsion increases the closer the electrons are to the central atom.
The electron density in a bond formed between the central atom and a very
electronegative atom will be polarized away from the central atom and will be less
effective in repelling electrons than if the central atom was bonded to an element with
lower electronegative.

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b. Therefore, bond angles involving very electronegative will tend to be smaller than those
involving less

c. Example.

O O

C C
F F H H
108 ' 118 '

2. When lone pairs are present, the bond angles decrease as the size of the central atom increases.

N P As
H H H
H H H
H H H
107 ' 94 ' 92 '

III. Hybridization
A. General
1. Covalent bonds are formed by the overlap of orbitals on adjacent atoms. The greater the
extent of overlap, the stronger will be the resulting bond. In comparing the shapes of
molecules from VSEPR and the orientation of the atomic orbitals on a central atom that
can be used in forming bonds (s, px, py, pz, dz2 , dx2-y2, dxy, dxz, dyz), it is apparent that
the atomic orbitals alone will not give the most efficient overlap.
a. Greater overlap, and hence stronger bonds, can be obtained by replacing the atomic
orbitals with a set of orbitals whose lobes of maximum probability point directly along
the bonding axes.
b. These orbitals can be generated by taking suitable linear combinations of the atomic
orbitals. Orbitals obtained in this way are called hybrid orbitals and the atom is said
to be hybridized.
2. Since the lone pairs (L) and atoms bonded (B) to a central atom determine the geometry
around the atom (from the VSEPR theory) the number of hybrid orbitals needed will be
L+B.
B. Types of hybrid orbitals.
1. L + B = 2. Linear arrangement.
a. Will need two hybrid orbitals whose lobes of maximum probability point in opposite

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directions. Assuming the bonding axis is the x axis, these hybrids can be obtained by
adding and subtracting the s and the px orbitals as shown below.

! SP2 = "S + "Px ! SP2


"P x

!SP1
!SP1= "S - "Px
"S

(The shaded areas represent a negative sign and the white a positive sign)

b. Each hybrid orbital has 50% s and 50% p character. They are called sp hybrid
orbitals and the atom is said to be sp hybridized.
c. Consider BeCl2 it is a linear molecule. The Lewis diagram is | Cl−Be−Cl |
The Be has two atoms bonded and no lone pairs (L+B=2). The Be is sp hybridized
and the overlaps are as follows.
Cl Be Cl

1) The bonding can be thought of as taking place through the steps:

2s 2p 2s 2p
Be ↑↓ __ __ __ ⇒ ↑ ↑ _ _
⇓ sp hybridize
↑ ↑ _ _
sp sp py p z

The two half filled sp hybrid orbitals on the Be overlap with two half filled
orbitals on the Cl's to give the Be−Cl bonds.
2) These bonds formed by the "head on" overlap of orbitals are called σ(sigma)
bonds.
d. Consider C2H2. The Lewis diagram is H−C≡C−H
1) Around each carbon L+B=2, therefore each C is sp hybridized as follows

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2s 2p 2s 2p
C(s2p2) : ↑↓ ↑ ↑ _ ⇒ ↑ ↑ ↑ ↑
⇓ sp hybridization
↑ ↑ ↑ ↑
sp sp py pz

2) The σ bonding is:

H C C H

This accounts for the carbon-hydrogen single bonds and one of the
carbon-carbon bonds.
3) The other two carbon-carbon bonds come about through the overlap of the
unhybridized carbon p orbitals as depicted below.

Pz
Z Z

Py
py
Y

X X

4) A bond formed by this type of "sideways" overlap of two orbitals is called a


π (pi) bond. The overlap is not nearly as efficient as that found in σ bonds.
Therefore, π bonds are weaker than σ bonds.
All single bonds are σ bonds.
Triple bonds are composed of 1σ and 2π bonds.

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Therefore, although a triple bond is stronger than a single bond, it is not three times as
strong.

d. Whenever L+B=2 for an atom it is sp hybridized. The atom may also form two π
bonds. Examples: HCN, CO2
2. L + B = 3. Planar trigonal arrangement.
a. Consider BF3. The Lewis diagram is
|F|
|
B−F|
|
|F|
1) The boron has three atoms bonded and no lone pairs. The molecule is trigonal
planar. The F−B−F bond angles are 120°.
2) Assuming that the molecular plane is the xy plane, The s, px and py orbitals can be
combined to give three equivalent sp2 hybrid orbitals. Their lobes of maximum
probability are in the same plane and are oriented at 120° from one another.

!sp2 (1)
!sp2 (2)

!sp2 (3)
The hybridization sequence is
2s 2p 2s 2p
B(2s22p1): ↑↓ ↑ _ _ ⇒ ↑ ↑ ↑ _
⇓ sp2 hybridization
↑ ↑ ↑ _
sp2 sp2 sp2 pz
The vacant pz orbital is oriented above and below the molecular plane.
b. Consider C2H4. The Lewis diagram is H H
C=C
H H

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1) Each carbon is bonded to three other atoms and has no lone pairs. The carbons are
sp2 hybridized in the same way as was the B in BF3. The difference is the each
carbon has four electrons, three in the sp2 hybrid orbitals and one in the
unhybridized pz orbital.
C ↑ ↑ ↑ ↑
sp2 sp2 sp2 pz
2) The σ bonding is

H C H

H
H

3) The pz orbitals can overlap to form a π bond.

H H

H H

4) A double bond is composed of 1σ + 1π bond.


c. Whenever L+B=3 the central atom is sp2 hybridized. Examples:
- -
SO3, NO2 , NO3 , BH3
3. L + B = 4. Tetrahedral arrangement.
a. Consider CH4. The Lewis diagram is H
|
H-C-H
|
H
1) The carbon has four atoms bonded and no lone pairs. The molecule is tetrahedral and
the H−C−H bond angles are 109°28". The s, px, py, and pz orbitals can be combined

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to give four equivalent sp3 hybrid orbitals oriented along the tetrahedral lines.
2) The hybridization sequence is
2s 2p 2s 2p
2
C2s 2p 2 ↑↓ ↑ ↑ _ ⇒ ↑ ↑ ↑ ↑
⇓ sp3 hybridization
↑ ↑ ↑ ↑
sp3 sp3 sp3 sp3
3) The carbon forms four σ bonds.
b. Whenever L+B = 4 the central atom will be sp3 hybridized. Examples
2- + 2-
NH3, SO4 , NH4 , C2H6 (both C's sp3 hybridized), H2O, SO3
4. L + B = 5. Trigonal bipyramidal arrangement
a. Consider PF5. The Lewis diagram is
F

F
F P
F

1) Phosphorus forms five single bonds and has no lone pairs. Therefore, it needs
five hybrid orbitals. These can be obtained by hybridizing the 3s, 3p and one
3d atomic orbitals.
3s 3p 3d
2 3 0
P(3s 3p 3d ): ↑↓ ↑ ↑ ↑ _ _ _ _ _

↑ ↑ ↑ ↑ ↑ _ _ _ _
3
⇓ dsp hybridization
↑ ↑ ↑ ↑ ↑ _ _ _ _
dsp3 hybrids d orbitals
2) The five hybrid orbitals are not equivalent. The three in the equatorial plane
are essentially sp2 hybrids and the two axials are dp hybrids. If the equatorial
plane is the xy plane, then the s, px and py orbitals hybridize to form the sp2
equatorial hybrids, while the pz and dz2 orbitals combine to give the two axial dp hybrids.
b. Whenever L+B=5 the central atom is dsp3 hybridized. Examples:
BrCl3, XeF2, SCl4

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5. L + B = 6. Octahedral arrangement.
a. Consider SF6 . The Lewis diagram
F

F S F

1) The sulfur forms four single bonds and has no lone pairs. Therefore, it needs six
hybrid orbitals. These can be obtained by mixing the 3s, 3p and two of the 3d atomic
orbitals to give six equivalent d2sp3 hybrid orbitals.
2) The hybridization sequence is: (assume that the F's are on the Cartesian axes)
3s 3p 3d
2 4
S 3s 3p 3d :0 ↑↓ ↑↓ ↑ ↑ _ _ _ _ _

↑ ↑ ↑ _ _ _
↑ ↑ ↑
⇓ d2sp3
hybridization
↑ ↑ ↑ ↑ ↑ ↑ _ _ _
d2sp3 hybrids d orbitals
The two d orbitals used are the dz2 and the dx2-y2.
6. There are other ways to describe the bonding in the hypervalent main group compounds
that might be better, but we will use the formalism of the electron pair bonds and dsp3 or
d2sp3 hybridization.

IV. Bond and molecular polarity.


A. Bond polarity.
1. Whenever two unlike atoms share electrons they will not share them equally.
a. The electron density in the bond is polarized towards the more electronegative
element.
b. The less electronegative atom will develop a partial positive charge (δ+) and the
more electronegative atom will develop a partial negative charge (δ-).
2. Example: χF > χH (use to show the direction of the polarization)

δ+ δ-
H F
a. The bond is a polar bond and the covalent bond is said to possess

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some ionic character.
b. Can use the concept of resonance to explain this polarity by including an ionic
form in the resonance hybrid.
[ H − F ↔ H+ F- ]
covalent ionic
c. The two forms do not contribute equally, the greater the difference in electronegativity
the more important will be the ionic term.
3. Ionic character in a bond tends to make the bond stronger.
B. Polar molecules.
1. Bond polarity can give rise to an overall polarity in the molecule.
a. One end of the molecule will be positive and the other end will be negative.
b. The molecule is said to be a polar molecule.
c. Polar molecules will tend to orient themselves in an electric field. This effect can be
measured and the dipole moment, µ, of the molecule can be determined. For a
system of two equal but opposite charges (δ) separated by a distance (r), the dipole
moment is given by:
+! "!
r
dipole moment = µ = !r
The dipole moment is a vector quantity pointing in the direction of the negative charge;
this is the net direction of polarization. The unit of dipole moment is the debye (D).
1 D = 3.33x10-30 Cm
d. Nonpolar molecules have µ = 0.

2. Diatomic molecules that have polar bonds will always be polar molecules. The polarity
reflects the difference in electronegativities. For example, consider the hydrogen halides
( χH = 2.1)

Compound χ(halogen) µ, D
HF 4.0 1.92
HCl 3.0 1.08
HBr 2.8 0.78
HI 2.5 0.38

3. For polyatomic molecules, the shape of the molecule, in addition to bond polarity, must
be considered. In some cases the polarity of one bond will cancel the polarity of another.
Therefore, it is possible for molecules that have polar bonds to be nonpolar.

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a. Examples
H
O O
H
H N O
O C O S
S
H O
H O O

polar polar nonpolar nonpolar polar


µ = 1.46 D µ = 1.87 D µ=0 µ=0 µ = 1.60 D

b. All of the above molecules have polar bonds. However, in CO2 and SO3 the oxygen
atoms are arranged symmetrically around the central atom and the polarities of the
bonds cancel out. When lone pairs are present on the central atom, it usually means that
the other atoms are not symmetrically distributed and the molecule will be polar.
c. If more than three different elements are present, the molecule could be polar even
though there are no lone pairs on the central atom. Example:

H Cl

C C
H H
H H
H H
Polar
Nonpolar µ=1.87 D
µ=0

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Valence Bond Theory Problems

1. Draw Lewis diagrams for the following covalent molecules and ions.
2. Some of the substances exhibit the phenomenon of resonance. Indicate which ones do and
show the Lewis diagrams for the resonance forms.
3. State which hybrid orbitals each central atom uses in bonding.
4. Based on (3) above, describe or sketch the shape of each molecule or ion. Estimate the angles
between bonds.

SF3- PO33- CS2 PCl4-


SO42- CO N2H2 SCN- (C central)

SO32- CO2 BF3 C2H6


SO3 CO3 2- NO2 + CH2O
SO2 BO33- N3- CH3OH (C central)

S2O32- (one S central) NH4 + O3 ClO3 -

NO3- NH3 CN- ClO2-


NO2- N2H4 CN22- ClO-
NF3 PO43- BrF3 SiCl4
XeF2 HCN BrF5 C3H6

5. Which of the above substances have polar bonds? Give the direction of polarization of these
bonds. Which substances are polar.

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