The steps in converting a molecular formula into a Lewis structure.

show bonding b w
ME
I
of valencee atoms in molecule

outeratom 1st
skeletalstructure
arrangementofatms then centralatom

valence e

D all
atomshave
feet

10-1
 Multiple Bonds double or triple

bond

If there are not enough electrons for the central atom

to attain an octet, a multiple bond is present.

Step 5: If the central atom does not have a full octet, change a
lone pair on a surrounding atom into another bonding pair to the
central atom, thus forming a multiple bond.

002 4 26 16ve

leftover
off D C
Q
this is an example
thisstepme of multiple bond
yed alle
10-2 carbon is missing let
 Resonance Structures whenthere is multiple

bonds
O3 can be drawn in 2 ways: ofbonds
a
B 1.5
double single

Tfo

These are two different reasonable Lewis structures for

the same molecule.

Neither structure depicts O3 accurately, because in reality

the O-O bonds are identical in length and energy.

we dont have a double and single bond in ozone but two identical

bonds w Bo 1.5 shorterthan single longer than double

10-3
 Electron Delocalization
E inside
Lewis structures depict electrons as localized either on an
individual atom (lone pairs) or in a bond between two
atoms (shared pair).

In a resonance hybrid, electrons are delocalized: their

density is “spread” over a few adjacent atoms.

ifresonance e
distributed evenly
I

10-4
 Fractional Bond Orders

Resonance structures often have fractional bond orders

due to partial bonding.

3 electron pairs
For O3, bond order = = 1½
2 bonded-atom pairs

10-5
 Formal Charge canalso tell s
the best lens structure
Formal charge is the charge an atom would have if all
electrons were shared equally.
Formal charge of atom =
# of valence e– - (# of unshared valence e– + ½ # of shared valence e–)
FC valence e binds nonbonding e

For OA in resonance form I, the formal charge is given by

6 valence e– - (4 unshared e– + ½(4 shared e–) = 6 – 4 – 2 = 0

10-6
 Formal Charge

Formal charges must sum to the actual charge on the

species for all resonance forms.

OA [6 – 4 – ½(4)] = 0 OA [6 – 6 – ½(2)] = –1
OB [6 – 2 – ½(6)] = +1 OB [6 – 2 – ½(6)] = +1
OC [6 – 6 – ½(2)] = –1 OC [6 – 4 – ½(4)] = 0

For both these resonance forms the formal charges sum to zero,
since O3 is a neutral molecule.

10-7
 Choosing the More Important Resonance Form
minimize FC
• Smaller formal charges (positive or negative) are
preferable to larger ones.

• The same nonzero formal charges on adjacent atoms are

not preferred.
Avoid like charges on adjacent atoms.

• A more negative formal charge should reside on a more

electronegative atom.
look EN table thehigher
the the more EN theatom

10-8
 each atom has 8e
Exceptions to the Octet Rule around it

Molecules with Electron-Deficient Atoms

H only wants
1 bond
B and Be are commonly
electron-deficient.
wants 2bonds
wants 3bonds
Odd-Electron Species

A molecule with an odd number of electrons is

called a free radical.

10-9
 Exceptions to the Octet Rule

Expanded Valence Shells

An expanded valence shell is only possible for nonmetals

from Period 3 or higher because these elements have
available d orbitals.

10-10
 once we have lewis stature we can use that information to det
gffney
Valence-Shell Electron-Pair Repulsion Theory
(VSEPR)

Each group of valence electrons around a central atom is

located as far as possible from the others, to minimize
repulsions.

A “group” of electrons is any number of electrons that

occupies a localized region around an atom.
A single bond, double bond, triple bond, lone pair, or single electron all
count as a single group.

nitrogenhas
carbon has 2
H 4 e groups
gramps double
abend central
binds
10-11 atom
 the of e groups canbe used to det molecular shapes
Electron-group repulsions and molecular shapes.

linear trigonal planar tetrahedral

2grups 3groups 49mn15

trigonal octahedral
bipyramidal a

10-12
 Electron-group Arrangement vs Molecular Shape
e domain geometry
The electron-group arrangement is defined by both
bonding and nonbonding electron groups. around the central
atom

The molecular shape is the three-dimensional

arrangement of nuclei joined by the bonding groups. This
is defined only by the relative positions of the nuclei.

Molecular shape is classified using the designation

A = central atom
AXmEn X = surrounding atom
E = nonbonding valence-electron group
m and n are integers onthe central atom

10-13
 Bond Angle in addition to describing
not geometry
The bond angle is the angle formed by the nuclei of two surrounding
atoms with the nucleus of the central atom.
each molecular geometry

have predictalle
bond angles
120

The angles shown in Figure 10.2 are ideal bond angles, determined by
basic geometry alone. Real bond angles deviate from the ideal value in
many cases. canbe due to multiple bonds or tone of e on central
X Y Z atom

:
A A A A
X X X X X X X X
real = ideal real ≠ ideal real ≠ ideal real ≠ ideal

10-14
 The single molecular shape of the linear electron-group arrangement.

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

AX2

Examples:
CS2, HCN, BeF2

2 e groups at binds
and no non bindinge
on central atom

This key refers to Figures 10.3 through 10.8.

10-15
 The two molecular shapes of the trigonal planar 3 e domains
electron-group arrangement.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

AX3

Examples:
SO3, BF3, NO3–, CO32–

3 outer atom or
3 binding groups

AX2E e pair
Examples:
2 outeratoms or
SO2, O3, PbCl2, SnBr2
2 bindinggroupsu
I pair of e

10-16
 Factors Affecting Bond Angles tree is
predicable bad

angle for each

Nonbonding (Lone) Pairs molecular geometry

A lone pair repels bonding pairs more

strongly than bonding pairs repel each
other. This decreases the angle between
the bonding pairs.

95 bc of LPofe
Double Bonds

A double bond has greater electron

density than a single bond, and repels
the single bond electrons more than they
repel each other.
lone pair of e can ease shiftinbondangles

10-17
 The three molecular shapes of the tetrahedral
electron-group arrangement.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

AX4
Examples:
CH4, SiCl4,
SO42–, ClO4–
4outeratoms or a bonding
groups

2lonepairof
e
AX3E AX2E2
Ie pair
Examples: Examples:
NH3, PF3 H2O, OF2, SCl2
ClO3–, H3O+
2bonding gramps
3bindingaromas zine pair e
1lonepaire

10-18
 The four molecular shapes of the trigonal bipyramidal
e domain electron-group arrangement. 5 e domains
geometry
2 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

AX5 Examples: AX4E Examples:

PF5, AsF5, SF4, XeO2F2
SOF4 IF4+, IO2F2–
5binding
domains

AX3E2 AX2E3
Examples: Examples:
ClF3, BrF3 XeF2, I3–, IF2–

2 bindingdomain
3 lone pairof e

10-19
3bondingdomain 174m key
2Ime account of bonding
 I 9
and non bonding
domains

Axial and Equatorial Positions

A five electron-group system has two different positions for

electron groups, and two ideal bond angles.

Equatorial-equatorial repulsions are

weaker than axial-equatorial repulsions.

Where possible, lone pairs in a five electron-group system

occupy equatorial positions. to minimize repulsions

10-20
 The three molecular shapes of the octahedral
electron-group arrangement.

AX6
Examples:
SF6, IOF5

AX5E AX4E2

Examples: Examples:
BrF5, TeF5–, XeF4, ICl4–
XeOF4
AXuE
Shindingdomain 4bindingdomain
10-21 I love pair nonbondingdomain 2 me pair nonbinding domain
 Molecular shapes for central atoms in Period 2 and
in higher periods.

Pyramidal
tetrahedral Trisffirand

hentz
seesaw
trigant
linear ftp.amid

pilinan F shape

Hahedral

10-22
 A summary of common molecular shapes with two to six
electron groups.

10-23
10-24
Chemistry 1A Molecular Geometries Worksheet

Molecular Geometry Worksheet: VSEPR Theory, Orbital Hybridization, and Molecule Polarity

Correlation Table
Electron Electron-Domain Predicted Bond Orbital Hybridization of Bonding Nonbonding Molecular Geometry
Domains Geometry of Atom Angle(s) Atom Domains Domains of Atom
2 Linear 180° sp 2 0 Linear
3 0 Trigonal planar
3 Trigonal planar 120° sp2
2 1 Bent
4 0 Tetrahedral
4 Tetrahedral 109.5° sp3 3 1 Trigonal pyramidal
2 2 Bent
5 0 Trigonal bipyramidal
5
90° axial, 120° 4 1 Seesaw
(expanded Trigonal bipyramidal sp3d
equatorial 3 2 T-shaped
octet)
2 3 Linear
6 6 0 Octahedral
(expanded Octahedral 90° sp3d2 5 1 Square pyramidal
octet) 4 2 Square planar

Polar Molecule Guide

Are there polar
bonds present?
NO
Are there lone
pairs on the NO Molecule is
Benttriganol Pyramid
|∆EN| ≥ 0.5? central atom? NONPOLAR
Seesaw Tshaped
YES YES YES

Are polar bonds

arranged so they cancel?
Are lone pairs
on central YES Molecule is
sq pyramid always
(Vector sum is zero? Check
direction and magnitude of
atom arranged
so they cancel?
NONPOLAR dipole polar
polar bonds.) molecules
NO
NO
Molecule is
Molecule is Weakly POLAR
POLAR

Molec Geom Worksheet.doc i Last Modified 4/5/12

 The four steps in converting a molecular formula to a
molecular shape

Molecular Step 1 Draw Lewis structure.

Formula

Lewis Step 2 Count all e- groups

around central atom (A). Phystithorksheet
structure

Electron- Step 3 Note positions of any lone

group pairs and double bonds.
arrangement
Step 4 Count bonding and
nonbonding e- groups
Bond separately.
angles

Molecular shape
(AXmEn)
10-25
 in the lewis structure worksheet we talked about bond polarity

Molecular Shape and Molecular Polarity

of e in the entiremolecule
overalldist
g
Overall molecular polarity depends on both shape
and bond polarity.

The polarity of a molecule is measured by its dipole

moment (μ), which is given in the unit debye (D).

A molecule is polar if
- it contains one or more polar bonds and
- the individual bond dipoles do not cancel.
the molecular geometry 4 lone pair of e to make the
molecule asymmetrical will result in a dipole

10-26
 The orientation of polar molecules in an electric field.

this molecule is polar

the molecules
will arrange
Molecules are randomly oriented. Molecules become oriented themselves
when the field is turned on. according
to polar
10-27
 Bond Polarity, Bond Angle, and Dipole Moment
polar police
Example: CO2

The DEN between C (EN = 2.5) and O (EN = 3.5) BEN 3.5 2.5
makes each C=O bond polar. 1 0
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Lewis Structure
Molgeometryis likar

CO2 is linear, the bond angle is 180°, and the

individual bond polarities therefore cancel. The
molecule has no net dipole moment (μ = 0 D).
some geometries will always be non polar molecule if the outer atoms
are the same b c the bind polarites cancel
10-28 Linear Trigand Planar Tetrahedral
 Trigand Bipyramid octahedral
no dipole if outer atomsarethe
Bond Polarity, Bond Angle, and Dipole Moment same

AEN 1.4 thisisapolar bud

Example: H2O 2 Is
The DEN between H (EN = 2.1) and O (EN = 3.5)
makes each H-O bond polar.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Mol geometry
Bent
8 thedipole
do not
cancel
St St
H2O has a V shaped (bent) geometry and the individual
bond polarities do not cancel. This molecule has an
overall molecular polarity. The O is partially negative
while the H atoms are partially positive.

10-29
 Bond Polarity, Bond Angle, and Dipole Moment

Molecules with the same shape may have different polarities.

Both of these
CCl4 CHCl3 moleculeshave
all theouter tetrahedral
atomsare geometry
same
bonds cancel C H bond is
eachother notequivalent
out_ to C 4 so
Bonds are polar, but individual Bond polarities do not cancel. This
bond polarities cancel. molecule is polar (μ = 1.01 D).
non polar they do not
molecule cancel
no dipole polar molecule
Dipole
10-30
 The Effect of Molecular Polarity on Behavior
Example: The cis and trans isomers of C2H2Cl2

there is
no overall
a dipole
dipole

thebonddipoles
thebond dipole cancel out
do Wffancel
The cis isomer is polar while the trans isomer is not.
The boiling point of the cis isomer is 13ºC higher than
that of the trans isomer.

10-31
 The influence of atomic properties on macroscopic
behavior.
structure vs funtime thestructure of a
molecule can affect the behavior of
the sale molence Chem IB IC

ordipole

strutne Molgeometry Dispersin

Lewis
non polar molecules

How to draw lens structure Dipole

polar molecule
Det not geometry
Bad and molecular polarity O N strongdipole

10-32
atomic orbitals SP dit Hybrid Orbitals can bedetermined y

1,3 5,7 the of e groups

will take atomic orbitals and hybridise according to e groups
• Mixing the s and p orbitals yields two degenerate orbitals
that are hybrids of the two orbitals.
– These sp hybrid orbitals have two lobes like a p orbital.
– One of the lobes is larger and more rounded, as is the
s orbital.

any molecule Y
ze domain
10-33
 Hybrid Orbitals

• These two degenerate orbitals would align themselves

180° from each other. linear
• This is consistent with the observed geometry of beryllium
compounds: linear.
hybridization Sp

10-34
 Hybrid Orbitals

Using a similar model for boron leads to three

degenerate sp2 orbitals. Form 3 bonds or
3 e domain
groups we need
15 2 XD

sp2

10-35
 Hybrid Orbitals

With carbon, we
get four
degenerate sp3
orbitals.
4

10-36
 Valence Bond Theory

• Hybridization is a major player in this approach to

bonding. How do hybrid orbitals come together to form bonds in
• There are two ways orbitals can overlap to form bonds many
between atoms.
• Sigma (s) Bonds and Pi (p) Bonds

10-37
 Sigma (s) Bonds all single bonds are 0
overlap of hybrid
orbitals

• Sigma bonds are characterized by

– Head-to-head overlap.
– Cylindrical symmetry of electron density about the
internuclear axis.

10-38
 Pi (p) Bonds side to side overlap
6 from double or
triple bond

• Pi bonds are characterized by

– Side-to-side overlap. double or
triplebond
– Electron density above and below the internuclear
axis.

10-39
 Single Bonds

Single bonds are always s bonds, because s overlap is

greater, resulting in a stronger bond and more energy
lowering.

10-40
 Multiple Bonds

In a multiple bond, one of the bonds is a s bond and the

rest are p bonds.

10-41
 Multiple Bonds

o overlap b w
hybridorbitals
4 I unnybridted
p orbitals

• In a molecule like formaldehyde (shown at left), an

sp2 orbital on carbon overlaps in s fashion with the
corresponding orbital on the oxygen.
• The unhybridized p orbitals overlap in p fashion.

10-42
 Multiple Bonds

In triple bonds, as in
acetylene, two sp orbitals form
a s bond between the
carbons, and two pairs of p
orbitals overlap in p fashion to
form the two p bonds.
T
12
o sp is Iftsp o o sp is

10-43 Sp SP
 IIinas
of
each
geometry

of e domains is the same

as of

e domain geometry is different

not
 go by
onepairof

I
Chemistry 1A
Effy
Molecular Geometries Worksheet

fifi
Molecular Geometry Worksheet: VSEPR Theory, Orbital Hybridization, and Molecule Polarity

am nonmeeirs
Correlation Table
Electron Electron-Domain Predicted Bond Orbital Hybridization of Bonding Nonbonding Molecular Geometry
Domains Geometry of Atom Angle(s) Atom Domains Domains of Atom

0
2 Linear 180° sp 2 0 Linear

EE
3 0 Trigonal planar
3 Trigonal planar 120° sp2

0
2 1 Bent
4 0 Tetrahedral
4 Tetrahedral 109.5° sp3 3 1 Trigonal pyramidal
2 2 Bent
5 0 Trigonal bipyramidal
5
90° axial, 120° 4 1 Seesaw
(expanded Trigonal bipyramidal sp3d
equatorial 3 2 T-shaped
octet)
2 3 Linear
6 6 0 Octahedral
(expanded
octet)
Octahedral 90° sp3d2
e
5
4 o
1
2
Square pyramidal
Square planar

Polar Molecule Guide

g
Are there polar Are there lone
NO NO
bonds present? pairs on the Molecule is
|∆EN| ≥ 0.5? central atom? NONPOLAR

YES YES YES

Are polar bonds Are lone pairs

arranged so they cancel? on central YES Molecule is
(Vector sum is zero? Check atom arranged NONPOLAR
direction and magnitude of so they cancel?
polar bonds.)
NO
NO
Molecule is
Molecule is Weakly POLAR
POLAR
Do the buds cancel out
Polak overallshift of e
Molec Geom Worksheet.doc i Last Modified 4/5/12

non polar dipole cancel out

 no
I of e

AqÉÉ

Bonding
Thding
Ez
Chemistry 1A Molecular Geometries Worksheet

1A 8A
1 2
1 H He
1.008 2A 3A 4A 5A 6A 7A 4.003
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar
22.99 24.31 3B 4B 5B 6B 7B 8B 1B 2B 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.70 63.55 65.39 69.72 72.59 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 (209) (210) (222)
87 88 89 104 105 106 107 108 109 110 111
7 Fr Ra Ac Rf Ha Sg Ns Hs Mt
(223) (226) (227) (261) (262) (266) (262) (265) (266)

58 59 60 61 62 63 64 65 66 67 68 69 70 71
6 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.1 140.9 144.2 (145) 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
90 91 92 93 94 95 96 97 98 99 100 101 102 103
7 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lw
232.0 (231) 238.0 (244) (242) (243) (247) (247) (251) (252) (257) (258) (259) (260)

Molec Geom Worksheet.doc ii Last Modified 4/5/12

if the of e domains are

the same as of bonding domains
 the e domain
seretry
Lab section: MW or TTh Name:
mystify
Complete the following tables.
d if there is LP of e on central atomthe
Most Stable Number of Orbital 3-D drawing
Compound or Lewis Structure Electron Domain Molecular Polar or
Electron Hybridization of Molecular
Ion (according to formal Geometry Geometry nonpolar?
Domains notation Geometry
charge guidelines)

H 2O
..
H-O-H
..
4 Tetrahedral

I sp3 Bent

H
O

H
Polar

i
If E
NH3
4 tetrahedral sp3
pyramidal

AX4
83
CCl4
4 tetrahedral
tetrahedral

CO2
C 2 linear sp 0
lineak

HCN
2 linear linear
sp
Axz
SO2
3 trigand sp2
planar BILE
Molec Geom Worksheet.doc 1 Last Modified 4/5/12

AXE
Lab section: MW or TTh Name:

Most Stable Number of Orbital 3-D drawing

Compound or Lewis Structure Electron Domain Molecular Polar or
Electron Hybridization of Molecular
Ion (according to formal Geometry Geometry nonpolar?
charge guidelines)
Domains notation Geometry

BF3 É triganol trigand nonpolar

3 planar SP planar
D
PO43–
NA

5
PCl5
I 5 this
bipyramid Spd triganol
non polar
bipyramid
(around each C) (around each C) (for each C) (around each C)

C 3H 8

BrF5
6
octahedral
sp3d2 FEE polar
pyramidal
0 dipole

SF6
6 orchard sp3d2 heard

Molec Geom Worksheet.doc 2 Last Modified 4/5/12

Lab section: MW or TTh Name:

Most Stable Number of Orbital 3-D drawing

Compound or Lewis Structure Electron Domain Molecular Polar or
Electron Hybridization of Molecular
Ion (according to formal Geometry Geometry nonpolar?
charge guidelines)
Domains notation Geometry

SO32–
NA

BrO3–
NA

ii triganol AXYE
sp d
TeCl4
5 bipyramid seesaw

ClF3

x
XeF2

–
ICl4
NA

Molec Geom Worksheet.doc 3 Last Modified 4/5/12

Lab section: MW or TTh Name:

Molecular Geometry and Bonding Questions:

1. The molecule SO2 has a dipole moment, but CO2 does not. Sketch the geometry of these two molecules and use the sketches to help
you EXPLAIN these facts.

polarmolecule they hag 215.9648non polarmolecule

so 6 216 18
dipole cancel nodipole
5 2bonding I nonbinding If moment
domain
2bonding
non bonding
not geometry iBent
notgeometry
these dipoles donot
Linear
cancel
2. Make a three-dimensional drawing showing the geometry of the following molecules. On each sketch indicate the direction of the
molecule’s dipole moment, if any. If the molecule is nonpolar, write “nonpolar” next to your drawing.
(a) CH3F (b) SiF4 (c) NO2 (d) HCN

to
H H
O N
H EN.am
Dipole p p dp.ptEnthatom
poor G dipole

III
Sfmetrical
O
I
Molec Geom Worksheet.doc L 4 Last Modified 4/5/12

Both tetrahedral
Lab section: MW or TTh Name:

3. Give a bonding scheme using Valence Bond Theory for the following molecules. To do this,
a. draw the Lewis Structure for both molecules
b. label each bond in both Lewis Structures as sigma or pi
c. indicate the orbitals used by each atom to form each bond using the following notation: C(sp2)-C(sp2) overlap for the C-C
sigma bond, etc.
d. indicate the orbital(s) used for any lone pairs that exist.

(i) Phosphorous pentahydride, PH5 (ii) Ethylene, CH2CH2

Sx o bonds
I 1 clap C ZP fee m

p pSpd H Is one ans

if
nothybriane

sp sp2
C spa C spa
4. Dinitrogen difluoride exists in the following forms called cis and trans isomers (l.p. not shown). Explain in terms of Valence Bond
Theory and bond energies why the two different forms exist as separate molecules and do not interconvert at room temperature.

F F F 0 C spa H 13
N N N N
cis F trans

Molec Geom Worksheet.doc 5 Last Modified 4/5/12

Lab section: MW or TTh Name:

5. Make a three-dimensional drawing showing the geometry of

(a) a sulfuric acid molecule. (b) an acetic acid molecule.

42504 4124302 OR at cook

4 a
4

6. On your drawings indicate the hybridization of

(a) the sulfur atom in a sulfuric acid molecule. (c) the oxygen atoms in an acetic acid molecule.

(b) the oxygen atoms in a sulfuric acid molecule. (d) the carbon atoms in an acetic acid molecule.

Molec Geom Worksheet.doc 6 Last Modified 4/5/12