3 types of bonding

lewis dot
molecular geometry
 Schedule Chapters 8 & 9
Day Topic Homework
1 Electronegativity & Bond Type Ch 8 # 37, 38, 61, 62
Lewis Structures
2 Lewis Structures Ch 8 # 63-66, 73
3 Shapes & Polarity Ch 8 # 77-94
4 Hybrid Orbitals & Sigma/Pi Bonds Ch 9 # 15 – 30
5 Bond Enthalpies Ch 8 # 47-60, 71, 72
6 Bond Enthalpy Practice
7 Review FR Practice Exam
8 FR Exam MC Practice Exam
9 MC Exam Outline Chapter 10
 Chemical Bond
• A force of attraction that holds two
atoms together
• involves the valence electrons
 Chemical bond
• Valence Electrons – the electrons
in the outermost energy level of an
atom -

This Lithium
Atom has one + -

valence electron - + +
 The Octet Rule
• Atoms will combine to form compounds in
order to reach 8 valence electrons in their
outer energy level – most stable.

CONSIDER EIGHT A HAPPY NUMBER FOR

ATOMS!
 The Octet Rule In Action
6 7
-
-
-
Notice how this chlorine atom has
- - 7 valence electrons, one away
5
- -
from eight. It will try to gain one
more according to the Octet Rule.
++++
++ + +
- + ++ ++ -

+++ +
-
- -
4 -

- -
1 1
- -

- - -
- -
2
3
++++
++ +
Notice how the sodium atom has -
+ -

one valence electron. It is this ++ +

electron that it will try to get rid -

of according to the Octet Rule. - -

-

Where do you think Chlorine finds that one electron that it needs?
 Basics of Bonding
A chemical bond occurs when atoms or ions are
strongly attached to each other.
1. Ionic bonds involve the transfer of electrons (e-)
and the subsequent electrostatic attractions.
-- “metal/nonmetal” (“cation/anion”)
2. Covalent bonds involve the sharing of e–
between two atoms.
-- “nonmetal/nonmetal”
3.metallic bonds: each metal atom is
bonded to several neighboring atoms
-- bonding e– (i.e., valence e–) are free to move
throughout the material
Lewis symbols show ONLY the
valence e– (i.e., the ones
involved in bonding).

C N S

Gilbert Lewis
(1875–1946)
 Rules for Covalent Lewis Structures
• Duet Rule: atom only wants 2 valence electrons

1st energy level can only hold 2e-

so Hydrogen only needs to gain
1e- to be stable like Helium!

• Octet Rule: atom wants 8 valence electrons (all other atoms!!!)

Wants 8e- to be stable like the noble gas in their row!

 Dot Designations

Valence Electrons can be represented by Lewis Dot Structures.

1 valence e- 2 valence e- 3 valence e- 4 valence e-

X X X X
5 valence e- 6 valence e- 7 valence e- 8 valence e-

X X X X
Using Lewis Dot Structures to
Represent Ions
Sodium has 1 valence e-. When sodium becomes
an ion it loses one electron to have an octet like
the closest noble gas.

Na [Na] + e- +
Using Lewis Dot Structures to
Represent Ions
Fluorine has 7 valence e- . When Fluorine
becomes an ion it gains one electron to fill the
octet.

Add the lewis dots in your notes

F + e- [F] -
 Ionic Bonds (M+NM)
Ionic Bonds are always NM steals the e-
between a Metal (M) & away from the M
a Non-Metal (NM)

NM is (-) after
Metal is (+) after
gaining an e-
losing an e-

Opposite charges attract

The (+) M & the (-) NM
“Stick” together forming
an “ION”ic bond

Salt crystals form when

alternating (+) and (-) ions
“stick” together forming
layers of ionic bonds
Metals always lose electrons
• Metals have low ionization energy… they lose
electrons easily!
• The number of electrons lost is equal to the charge
of the metal ion.
• Metals always form + cations
Metals always lose electrons continued
• Type I Metals (simple) they always form the SAME
charge
• Type II Metals (complex) they form DIFFERENT
charges
+1
+2 +3
 METALS Always LOSE Electrons
• To become stable like the previous noble gas.

Na  1s 2s 2p 3s
2 2 6 1
Na 1  1s 2 2s 2 2p 6
Lost
Same as Neon

Ca  1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 Ca 2  1s 2 2s 2 2p 6 3s 2 3p 6
Lost
Same as Argon
Al  1s 2 2s 2 2p 6 3s 2 3p1 Lost Al3  1s 2 2s 2 2p 6
Same as Neon
• The number of electrons lost is equal to the charge of the metal ion.

• Metals always form + cations because they have very low ionization
 Ionic Bonding
Na(s) + ½ Cl2(g) NaCl(s)
“Salts” are brittle
– solids with high
Na + Cl Na+ + [ Cl ] melting points.
lattice energy: the energy required DHfo = –410.9 kJ/mol
to separate 1 mole of solid ionic
compound into gaseous ions
-- a measure of stability enthalpy
(i.e., heat)
NaCl(s) Na+(g) + Cl–(g) of formation
DHlatt = +788 kJ/mol
In general, ionically bonded substances have...
…big, (+) lattice energies.
Because lattice energies are electrostatic in nature,
two variables are involved in how big they are:

1. the magnitude of the charges (“wears the pants”)

2. the separation between the ions

Charge can easily be twice as large
(i.e., 2+ and 2– vs. 1+ and 1–), but the
separation never varies by that much.
Put the following in order of
increasing lattice energy: Now these:
LiBr, FeN, CdO. MgS, MgCl2, MgO.
LiBr < CdO < FeN MgCl2 < MgS < MgO
 With transition-metal ions, the e– lost first come
from the subshell with the largest value of n.

e.g., Ni = [Ar] 4s2 3d8

Ni2+ = [Ar] 3d8
Ni3+ = [Ar] 3d7

Recall that polyatomic ions are groups of atoms that

stay together and have a net charge.
-- e.g., NO3– CH3COO–
-- their atoms are held to each other by… covalent
bonds
Cations are smaller than the neutral atoms from
which they are derived.
e.g.,
Li 1s2 2s1 Li+ 1s2

-- orbitals might be completely vacated

-- e–/e– repulsion always decreases

Fe Fe2+ Fe3+
 Anions are larger than the neutral atoms from
which they are derived.
-- more e–/e– repulsion

Cl 17 p ,
+ Cl– 17 p+,
17 e– 18 e–

An isoelectronic series is a list of species having an

identical electron configuration.
e.g., N3–, O2–, F–, Ne, Na+, Mg2+, Al3+
(big radius) (small radius)

EX. Which has the Rb+ Sr2+ Y3+

largest radius?
(smallest Zeff) (largest Zeff)
 Covalent Bonds (NM + NM)
• When non-metal atoms bond they SHARE ELECTRONS

• Co = Sharing Valent = Valence Electrons

– Non-metals have high Ionization Energy & high
Electronegativity … don’t want to lose their electrons =
steal electrons!
 Covalent Bonding

-- atoms share e–

-- covalent (molecular)
compounds tend to be
+ +
solids with low melting
points, or liquids or gases (–) charge density

-- one shared pair = a single covalent bond

of e– (i.e., 2 e–)
-- two shared pairs = a double covalent bond
of e– (i.e., 4 e–)
-- three shared pairs = a triple covalent bond
of e– (i.e., 6 e–)
bond polarity: describes the sharing of e –
between
atoms
nonpolar covalent bond: e– shared equally
polar covalent bond: e– NOT shared equally

electronegativity (EN): the ability of an atom

in a molecule to
attract e– to itself
-- A bonded atom w/a large EN
has a great ability to attract e–. max. EN = 4.0 (F)
-- A bonded atom w/a small EN
min. EN = 0.7 (Fr)
does not attract e very well.
–

-- EN values have been tabulated. (see p. 308)

 Chemical Bonds & Electronegativity
just read…
• Power of an atom in a molecule to attract electrons to itself
– Ionic bonds (complete transfer of e-) = difference > 2.0
– Polar Covalent (unequal sharing of e-) = difference 0.2 < < 1.7
– Pure Covalent (equal sharing of e-) = difference < 0.2
– *Gap between 1.7 and 2.0 is a gray area…
• If compound contains a metal = ionic
• If compound contains all nonmetals = polar covalent
The DEN between bonded atoms approximates
the type of bond between them.

DEN < 2.0 nonpolar covalent

0.2 < DEN < 1.7 polar covalent
DEN > 2.0 ionic bond

As DEN increases,
bond polarity...increases.

DEN for a C–H bond = 0.4, so

all C–H bonds (such as those
in candle wax) are nonpolar.
 Polar Covalent Bonds
• Non-metals that SHARE ELECTRONS UNEQUALLY
– Different strength = Different electronegativity values

More EN atom has more

control of the electrons!
 Dipole Moments
Polar covalent molecules have a partial (–) and
a partial (+) charge and are said to have a
dipole moment.
Draw this is
your notes
d+ d– d+ d+
H–F H–F H H
partial
charge O
d–

big polarity = _____

big DEN = _____ big dipole moment
 Polar Covalent Bonds
Assign partial charges and illustrate the dipole moment for each bond
The line between the atoms is the covalent
bond to illustrate e- are being shared!
copy these four example into your notes with the EN Values

 +
 -
 + -
H—F Br—Cl
2.1 4.0 2.8 3.0

- + + -
N—H P—S
3.0 2.1 2.1 2.5
 Polar molecules tend to align themselves with each
other and with ions. Draw this is your notes, both

H– F NO3 – NH +

F – 4

H–F H NO3
H–F
– NH +
F 4

H–

H–
F
** Nomenclature tip: For binary compounds, the less
electronegative element comes first.

-- Compounds of metals w/high oxidation #’s (e.g., 4+ or

higher) tend to be molecular rather than ionic.
e.g., TiO2, ZrCl4, Mn2O7
 Non-Polar Molecules
• Bonds in S8 and P4 and O3
2.5
• Bond between C—S and P—H
2.5 2.5 2.1 2.1
 Non-Polar Molecules
• Diatomic molecule = two identical atoms bonded together
Ex: N2 H2 F2 O2 I2 Cl2 Br2

EN=3.5 EN=3.5

Never Have Fear Of Ice Cold Beverages

7-Up
 Covalent Bonds
Which bond is MORE polar?

H—F 4.0 - 2.1 = 1.9

2.1 4.0

C—H 2.5 - 2.1 = 0.4

2.5 2.1
 Practice Problems
Calculate the difference in electronegativity between
each atom & determine which bond is more ionic:
Metal + Nonmetal greatest EN difference
• CsBr Cs: 0.8 Br: 2.8 2.8- 0.8 = 2.0
• KBr K: 0.9 Br: 2.8 2.8-0.9= 1.9
• MgBr2 Mg: 1.2 Br: 2.8 2.8-1.2 = 1.6

Calculate the difference in electronegativity between

each atom & determine which bond is more polar:
• B—Cl or C—Cl B: 2.0 Br: 2.8 2.8- 2.0 = 0.8
C: 2.5 Cl: 3.0 3.0- 2.5 = 0.5
• P—F or P—Cl
P: 2.1 F: 4.0 4.0- 2.1 = 1.9
P: 2.1 Cl: 3.0 3.0- 2.1 = 0.9
 Chemical bonds are made with the valence e-
just read this slide
• Covalent bond = reaction between all non-metals
– All non-metals have a high electronegativity (strong Zeff)
– Share electrons (single, double, triple bonds)

Polar Non-Polar

Hydrogen
 Chemical bonds are made with the valence e-
• Ionic Bond = reaction between metal and non-metal
– Metal has low ionization energy… loses e- (weak Zeff)
– Non-metal has high electron affinity… gains e- (strong Zeff)

• Li = 1s22s1 ____
2s1

• F = 1s22s22p5 ____ ____ ____ ____

2s2 2p5

• The non-metal steals the electron from the metal & two ions form
 Practice Problems
• Use electron configurations to determine the formula of the
compound that exists when the following elements react.

1. Mg and Br MgBr2 [Ar]4s23d104p5

[Ne]3s2
2. K and Cl KCl
[Ar]4s23d104p5

3. Na and S Na2S

4. Ba and O
BaO
 Covalent Lewis Structures
1. Count the total number of valence e-
– Add negative charge
– Subtract positive charge
2. Determine the central atom
– Carbon Always
– Hydrogen Never
– Least electronegative atom
3. Connect terminal atoms to central atom with single bonds
4. Place lone e- pairs to satisfy octets until you run out of e-
5. Left over e- go to the central atom
6. Use double/triple bonds if necessary
7. Double check your work
– Must have correct total number of valence electrons
– Octet/duet rules must be satisfied
 Rules for Covalent Lewis Structures
A. Connect each atom to the central atom with a single bond
A single bond represents TWO e- being shared by each atom

B. Add the remaining valence electrons around each atom to obtain

the octet or duet rule.

C. Double check your work…

 Is the total # of valence electrons correct?
 Is each atom following the octet or duet rule?
 Rules for Covalent Lewis Structures
A.If necessary, rearrange the valence electrons to form:
Double bond represents FOUR e- being shared by each atom

Triple bond represents SIX e- being shared by each atom

B. Double check your work… again!

 Is the total # of valence electrons correct?
 Is each atom following the octet or duet rule?
 Covalent Bonding
• Sharing of electrons
• HCl covalent bond can also be illustrated with
a Lewis Dot Structures.

H H Cl Cl
Questions:
A bond (dash) replaced how many electron dots?
Why did scientist do this?
 You try it:
• Can you draw the Lewis Dot structure for
Cl2?
– Hint: Start with the Valence Electron Dot
Structure for two Cl atoms.

Cl Cl
Cl Cl
 Quantum Mechanical Model of
Covalent Bonding
• The H2 covalent bond can also be illustrated

H H
with valence electron dot structures.

H H
The two electrons between the atoms are shared in a covalent bond.
Chemist use a line to represent 2 electrons in a covalent bond.
These drawings are called Lewis Dot Structures.
 Drawing Lewis Dot Structures
• Step 1: Count the total number of valence
electrons from all the atoms in the molecule.
• Example: H2O
2 H atoms 2 x 1e- = 2e-
1 O atoms 1 x 6e- = 6e-
Total number of valence e- = 8e-

The Lewis Dot Structure of H2O will have 8 electrons.

 Drawing Lewis Dot Structures
• Step 3: Subtract the number of electrons used to
make the skeleton structure from the total number of
valence electrons.
– How many electrons are in the skeleton structure? 4
• Step 4: Add the remaining electrons as lone pairs as
evenly as possible on all atoms except hydrogen.

Total number of valence e- 8e-

Minus electrons used in skeleton - 4e-
Electrons remaining to be added = 4e-

H O H
Add as
Lone Pairs
 Drawing Lewis Dot Structures
• Step 5: Check for Octets
– Are there 8 electrons around all atoms (except
hydrogen)?
2
8 4
H O H
6
If NO, use lone pairs to make
If YES, you are finished!
double or triple bonds.
 Lewis Dot Structure for O2
• Let’s draw the Lewis Dot Structure for Oxygen
• Oxygen atoms have 6 valence electrons.
• We will rotate the electrons so they can form bonding pairs

O
We use lines to represent shared electron pairs.
O
When atoms are bonded with 2 pairs of electrons it is called a
double bond.
Double Bond

O O
 Lewis Dot Structure for O2
• Let’s draw the Lewis Dot Structure for Oxygen
• Oxygen atoms have 6 valence electrons.
• We will rotate the electrons so they can form bonding pairs

O C O
We use lines to represent shared electron pairs.
When atoms are bonded with 2 pairs of electrons it is called a
double bond.
Double Bond

O C O
 Quantum Mechanical Model of
Covalent Bonding
• The CH4 covalent bond can also be illustrated
with a Lewis Dot Structures.

H H C C
 H|
H-C-H
|
H
 Lewis Dot Structure for N2
• Let’s draw the Lewis Dot Structure for Nitrogen
• Nitrogen atoms have 5 valence electrons.
• We will align the electrons so they can form bonding pairs

N N
We can use lines to represent shared electron pairs.
When atoms are bonded with 3 pairs of electrons it is called a
triple bond.
Triple Bond

N N
 Practice Problems
Draw the Lewis dot structures for the following:
1. PCl3

2. CH2Cl2

3. HCN
 Lewis Structures with CHARGES +/-
• POLYATOMIC IONS = covalent molecule (all NM) that has an
overall charge! Count valence e- and include charge.
– Ammonium Nitrate Carbonate Phosphate
NH4+1 NO3-1 CO3-2 PO4-3

• The charge on the molecule affects the TOTAL # of valence

electrons for Lewis dot.
• When the charge is (-) you ADD electrons
• When the charge is (+) you subtract electrons

5+(1x4) – 1 = 8e- 4+(6x3) + 2 = 24e-

5+(6x3) + 1 = 24e- 5+(6x4) + 3 = 32e-
 Lewis Structures with CHARGES +/-
Draw Lewis structure into your notes for ammonium NH4+ (8 e- dots)

Must put charge in

Upper right corner

Must put structure in [brackets]

• Draw the Lewis structure for nitrate NO3- = (24 e- dots)

N must share Some Lewis structures have

2 more e- for octet charges & resonance!
 Practice Problems
Draw the Lewis dot structures for the following:
3. SO32-

4. NH4+

5. C2H4
Just read and reviewLewis Structures
(or “electron-dot structures”)
1. Sum the valence e– for all atoms. If the species is an
ion, add one e– for every (–); subtract one e– for every (+).
2. Write the element symbols and connect the
symbols with single bonds.
3. Complete octets for the atoms on the exterior of
the structure, but NOT for H.
4. Count up the valence e– on your L.S. and compare
that to the # from Step 1.
-- If your LS doesn’t have enough e–, place as many e–
as needed on central atom.
-- If LS has too many e– OR if central atom doesn’t have
an octet, use multiple bonds.
 Resonance Structures
• When more than one correct Lewis structure can be written for the
same molecule/ion
– Arrangement of atoms is the same… only the e- placement differs
• Actual structure is the average (blend) of all the resonance structures
– Color green is a blend of blue and yellow
• All possible resonance structures must be written with a  to
separate them

• Example: Ozone (O3)

• Ozone has two equivalent O—O bonds whose length is intermediate

between a single O—O bond and a double O=O bond.
Lewis Structures with RESONANCE just
read this
When to check for resonance…
slide
1. When the Lewis structure has a double or triple bond
2. When the molecule has 3+ atoms

H follows the duet rule

Resonance isn’t always possible…
Single bonds
identical so moving
them is pointless

No where else for No where else for

the triple bond to go the triple bond to go
 Practice Problems
1. Draw the Lewis structure for the nitrate ion, NO31-

2. Draw the Lewis structure for sulfur trioxide

3. Which molecule will have shorter bonds, SO3 or SO32-?

SO3 has a blend between single/double bonds due to resonance
SO32- only has single bonds.
Therefore, SO will have shorter bonds.
 Formal Charges
• The preferred Lewis structure is the one where…
– The more electronegative element has the (-) charge
– The formal charges of the atoms are closest to zero
• Formal charge = V – (n + b/2)
– V = valence e- for the atom
– n = lone pair e-
– b = bonding e- (single=2e-; double=4e-; triple=6e-)

Example: CO2

– C = 4 – (0 + 8/2) = 0 C = 4 – (0 + 8/2) = 0
– O = 6 – (4 + 4/2) = 0 O = 6 – (6 + 2/2) = -1
– O = 6 – (4 + 4/2) = 0 O = 6 – (2 + 6/2) = +1
 Practice Problem
• The cyanate ion (OCN-) has three possible Lewis
structures.
– Draw these Lewis structures, and assign formal charges
to the atoms in each structure.

– Which Lewis structure is the preferred one?

 Exceptions to the Octet Rule
1. Incomplete Octet
– Less than octet rule
• Be & B (2nd period elements)
• BF3 vs. NH3BF3
– Odd-electron molecules
• Examples: NO = 11 e- & NO2 = 17 e-
2. Expanded Octet
• When the central atom is in or beyond the third period
• All atoms must follow octet rule first… any extra e- are placed on the
central atom
• Usually occurs when the terminal atoms are small and highly
electronegative: F, Cl, O
 Practice Problems
• Draw the Lewis dot structures for the following molecules/ions and
state how they violate the octet rule:
Chlorine dioxide
1. ClO2 Incomplete Octet odd electron molecules= 19 e

2. SF6
sulfur hexafluoride is expanded octet

Nitrogen dioxide
Incomplete octet, odd electron
molecules= 19 e
3. NO2
 Practice Problems
• Draw the Lewis dot structures for the following
molecules/ions and state how they violate the octet rule:
4. ICl4-
Tetrachloroidate ion
Expanded octet

5. O2- Super oxide incomplete

octet odd electron
molecule

6. BeF2

Beryllium fluoride
Incomplete octet less
than octet rule
 Shapes of Molecules
• Lewis structures help us determine the composition
of molecules and their covalent bonds but…
– They do not show us the shapes of molecules…
• The shape and size of a molecule combined with
the bond strength & polarity largely determine the
properties of a substance!
• Lewis structures combined with the rules governing
VSEPR theory can help us determine the shape and
polarity of a molecule…
• Covalent Molecules are 3-Dimensional; they have
SHAPES & bond ANGLES
 VSEPR Theory
• Valence Shell Electron Pair Repulsion
• Based on the fact that electrons want to maximize
their distance from one another to minimize their
repulsion 
 VSEPR Theory

• The # of electron domains is good starting point for

determining the shape of a molecule.
– e- domain is a region in which e- can be found
– Includes both bonding and non-bonding regions around
the central atom
– Single, double, or triple bonds count as one e- domain
 5 Differ Electron Domains
• How many e- domains does
the central atom have in
CO2, CH4, H2O, O3, O2?

• Electron Geometry…
– Tells the shape the e- take
around the central atom
• 2e- domains = linear
• 3e- domains = trig. planar
• 4e- domains = tetrahedral
• 5e- domains = trig. bipyramidal
• 6e- domains = octahedral
• Do ALL e- geometries have the
same molecular geometries?
Electron Domain Geometry
 Molecular Geometry

• Most e- domains have several

shapes as options
bonding pair
• Actual Molecular shape is
based on…
– # of non-bonding (lone) e-
– # atoms bonded
**based on central atom

lone pair
Takes up more space than a bonding pair.
 Determining VSEPR Shapes
1. Draw the Lewis dot structure for the molecule/ion

2. Count the total # of e- domains around central atom

• Each set of lone pair e- counts as one domain
• Single, double, and triple bonds count as one domain

3. Determine the # atoms bonded & the # lone pair e- around the
central atom

4. Determine the molecular geometry (shape)

5. Arrange the atoms so that the e- minimize their repulsion

• Atoms should point away from the lone pair e-
 Linear (180˚ Bond Angle)
Two Atoms Side by Side
– No central atoms… regardless of e- domains or type of bond
–• Regardless of single, double, triple
• Example: N2, H2, F2, O2, I2, Cl2, Br2, CO, NO, HF
Molecule only Linear (180˚)
has 2 atoms NO central atoms has
They must go
next to each 2 atoms bonded
other! 0 lone pairs
• When only 2 atoms in the compound only option is linear, bond angle
is 180˚ 
• Single, double, triple bonds act the same in VSEPR theory
 Linear (180˚ Bond Angle)
Two Electron Domains
– Central atom has 2 bonded atoms with 0 pairs of lone e-
– Example: BeF2 and CO2

Linear (180˚)
When the central atoms has
2 atoms bonded
0 lone pairs
 Linear (180˚ Bond Angle)
Five Electron Domains
– Central atom has 2 bonded atoms with 3 pairs of lone e
– Example: I3-1
 Trigonal Planar (120˚ Bond Angle)
Three Electron Domains
– Central atom has 3 atoms bonded with 0 lone pair e-
– Examples: BF3 and CO32-

Trigonal Planar (120˚)

When the central atoms has
3 atoms bonded
0 lone pairs
 Bent (120˚ Bond Angle)
Three Electron Domains
– Central atom has 2 atoms bonded with 1 lone pair e-
– Lone pair e- have enough room… they do not distort the angle
– Examples: O3 and SO2
 Tetrahedral (109.5˚ Bond Angle)
Four Electron Domains
– Central atom has 4 atoms bonded with 0 lone pair e-
– Examples: CH4 and SO42-

Tetrahedral (109.5˚)
When the central atoms has
4 atoms bonded
0 lone pairs
 Trigonal Pyramidal (107˚ Bond Angle)
Four Electron Domains
– Central atom has 3 bonded atoms with 1 lone pair e-
– lone pair e- takes up more space and pushes the atoms closer
together
– Example: NH3

Trigonal Pyramidal (107˚)

When the central atoms has
3 atoms bonded
1 lone pairs
 Bent (104.5˚ Bond Angle)
Four Electron Domains
– Central atoms has 2 bonded atoms with 2 pairs of lone e-
– 2 sets of lone e- take up more space and push the bonded atoms
even closer together
– Example: H2O
Bent (104.5˚)
When the central atoms has
2 atoms bonded
2 lone pairs
 Trigonal Bipyramidal (90˚ & 120˚ Bond Angles)
Five Electron Domains
– Central atom has 5 atoms bonded with 0 lone e-
– Examples: PF5 Phosphorus can EXCEED the OCTET
It’s in the 3rd energy level & has an empty “D” subshell

Trigonal Bipyramidal (90˚& 120˚)

When the central atoms has
5 atoms bonded
0 lone pairs
 See-Saw (90˚, 120˚, & 180˚ Bond Angles)

Five Electron Domains

– Central atom has 4 atoms bonded with 1 lone pair e-
– Lone pair e- have enough room… they do not distort the angles
– Examples: SF4
 T-Shaped (90˚ & 180˚ Bond Angles)

Five Electron Domains

– Central atom has 3 atoms bonded with 2 lone pair e-
– Lone pair e- have enough room… they do not distort the angles
– Examples: ClF3
 Octahedral (90˚ Bond Angle)
Six Electron Domains
– Central atom has 6 atoms bonded with 0 lone pair e-
– Example: SF6 Sulfur can EXCEED the OCTET
It’s in the 3rd energy level & has an empty “D” subshell

Octahedral (90˚)
When the central atoms has
6 atoms bonded
0 lone pairs
 Square Pyramidal (90˚ Bond Angle)
Six Electron Domains
– Central atom has 5 atoms bonded with 1 lone pair e-
– Lone pair e- do not distort bond angle
– Example: BrF5
 Square Planar (90˚ Bond Angle)
Six Electron Domains
– Central atom has 4 atoms bonded with 2 pairs of lone e-
– 2 pairs of lone e- do not distort the bond angles
– Example: XeF4
 Practice Problems
Determine the name, lewis dot, electron domain geometry &
molecular geometry of each of the following:
-1 Tin Chloride ion
1. SnCl 3 Electron domain geometry: Tetrahedral

Molecular geometry:
Selenium (II) chloride
2. SeCl2

3.phosgene
COCl2
EDG and MG: Trigonal planar
 Practice Problems
Determine the lewis dot,electron domain geometry &
molecular geometry of each of the following:

4. IF5
EDG: octahedral
MG square pyramidal

-1
5. ICl 4

EDG: tetrahedral
MG square planar
 Shapes of Large Molecules with
Multiple Central Atoms
• Determine shape of EACH central atom separately using the VSEPR theory.
– If an atom has 2 or more atoms bonded to it… it is considered a central atom!

• Example: Acetic Acid (CH3COOH)

Central Atom Carbon (on left) Carbon (on right) Oxygen

# of e- Domains 4 3 4
e- domain geometry Tetrahedral Trigonal planar Tetrahedral
Molecular Geometry Tetrahedral Trigonal planar Bent
Bond Angles 109.5 120 104.5
 Practice Problems
Determine the molecular shape and bond angles for
each central atom in the following molecules:
1. Poly (vinyl) alcohol: HOCH=CH2
Central Atom Oxyen Carbon #2 Carbon #3
# of e- Domains 2 2 4
e- domain Tetrahedral Trigonal Trigonal
geometry planar planar
Molecular Bent Trigonal Trigonal
Geometry planar planar
Bond Angles 109.5 120 120
 Practice Problems
Determine the molecular shape and bond angles for
each central atom in the following molecules:
2. Propyne: CH3CCH
Central Atom Carbon #1 Carbon #2 Carbon #3
# of e- Domains 2 2 4
e- domain Linear Linear Tetrahedral
geometry
Molecular linear linear Tetrahedral
Geometry
Bond Angles 180 180 109.5

Carbons #1 and 2 have a triple bond, linear geometry, 180°

Carbon # 3 has center of a tetrahedron, 109.5°

 Molecular Polarity
• The molecular geometry coupled with the electronegativity
values determine the overall polarity of a molecule.
1. Use electronegativity values to assign bond dipoles
• Bond dipole = vector arrow that points towards the more
electronegative atom

2. Analyze the molecular geometry to determine if vector

dipoles will cancel out.
 Molecular Polarity
No Net Dipole= Non-Polar Net Dipole= Polar
• When all the terminal atoms • When the terminal atoms have
have equal electronegativity different electronegativity
values AND the molecule is values OR the molecule is NOT
symmetrical (0 lone pair e-) symmetrical (1+ lone pair e-)
More Examples of Molecular Polarity
 Practice Problems
Assign bond dipoles and determine the molecular
polarity of each of the following:
1. OCS

2. NH3

3. CH2Cl2
 Valence Bond Theory
• VSEPR explains WHAT the shape is…
• Valence bond theory explains WHY the shape is…
– Covalent bonds are formed when the orbital of one atom shares space,
or overlaps, the orbital of another atom.
 Valence Bond Theory
• The VSEPR model illustrates that the bonds within a molecule are
identical yielding identical bond lengths and angles.

• If different orbitals (s, p, d) are involved in forming a covalent bond

how do the resulting bonds become identical?

– The orbitals of the central atom form identical ‘hybrid’ orbitals

before they overlap with the terminal atoms

• The hybrid orbitals are involved in forming the covalent bonds

• Hybrid orbitals are based on electron geometry NOT molecular

geometry 
 Hybrid Orbitals
• When orbitals of a given atom overlap they mix together to form new
‘hybrid’ orbitals
– The same # of orbitals will always be produced, but…
– Hybrid orbitals have a different shape than their original parent orbitals

– The new ‘hybrid’ orbital is what allows for the bonds within a molecule
to all be equal to one another
 Determining Hybridization
e- Domain Geometry # of Orbitals Hybrid Orbitals

Linear 2 sp

Trigonal Planar 3 sp2

Tetrahedral 4 sp3

Trigonal Bipyramidal 5 sp3d

Octahedral 6 sp3d2

• All electron geometries (regardless of molecular geometry) have the

same hybridization for the central atom.
 e- Geometry = Linear = sp Hybrid Orbitals
Be orbitals hybridize to form BeF2 Fluorine’s p-orbital overlaps
• Ground State with Be hybrid orbitals
• Fluorine
• Excited State
• Beryllium
• Hybridized Orbitals
e- Geometry = Trigonal Planar = sp2 Hybrid Orbitals

• BF3

• Boron’s orbitals are hybridized

 Fluorine’s p-orbital overlaps with B hybrid orbitals to

form a Trigonal planar molecule
 e- Geometry=Tetrahedral = sp3 Hybrid Orbitals

• CH4

• Carbons orbitals are hybridized

 e- Geometry=Tetrahedral = sp3 Hybrid Orbitals

• H2O

Oxygen’s orbitals are hybridized

 e- Geometry=Tetrahedral = sp3 Hybrid Orbitals

• NH3

• Nitrogen’s orbitals are hybridized

e- Geometry=Trigonal Bipyramidal = sp3d Hybrid Orbitals
• PCl5
• Phosphorus’s orbitals hybridize

• Chlorine’s p-orbital overlaps with the hybridized orbitals of

phosphorus to form PCl5
• All shapes with 5 e- domains around central atom form sp3d hybrid
orbitals… Trig. Bipyramidal, See-saw, T-shaped, and Linear
 e- Geometry=Octahedral = sp3d2 Hybrid Orbitals
• SF6

• Sulfur orbitals hybridize

• Fluorine’s p-orbital overlaps with the hybridized orbitals of sulfur

• All shapes with 6 e- domains around central atom form sp3d2 hybrid
orbitals… Octahedral, Square pyramidal, and square planar
 Determining Hybridization
e- Domain Geometry # of Orbitals Hybrid Orbitals
Linear 2 sp
Trigonal Planar 3 sp2
Tetrahedral 4 sp3
Trigonal Bipyramidal 5 sp3d
Octahedral 6 sp3d2

Predict the e- domain geometry and the hybridization of the central

atom in each of the following:
1. NH2-1 Trigonal planar 4 orbitals= sp3
Trigonal bipyramidal (seasaw)= 5 orbitals= sp3d
2. SF4
3. SO32- Trigonal planar 4orbitals= sp3

4. CO2 Linear 2 orbitals= sp

Trigonal planar 3 orbitals= sp2
5. H2CO
Ocatahedral 6 orbitals= sp3d
6. XeF
 Determining Hybridization
e- Domain Geometry # of Orbitals Hybrid Orbitals
Linear 2 sp
Trigonal Planar 3 sp2
Tetrahedral 4 sp3
Trigonal Bipyramidal 5 sp3d
Octahedral 6 sp3d2

Predict the e- domain geometry and the hybridization

of the central atom in each of the following:
1. NH2-1 Hybridization of NH2- ⇒ 1/2(V + M -C +A) ⇒1/2(5+2+1)= 4 orbitals= sp3
2. SF4 .Formula for hybridization
⇒ 1/2(V + M -C +A)
3. SO32- ⇒V = valence electron in central atom
⇒M = # of monoatomic atoms connected to the central atom
4. CO2 ⇒C =cationic charge
5. H2CO ⇒A = anionic charge
Sigma (σ) Bonds
• When orbitals overlap to form a bond that lies within the same plane
as the nucleus (inter-nuclear axis)
• All bonds (single, double, triple) contain at least one sigma (σ) bond

Pi () Bonds
• When orbitals overlap to form a bond in regions that lie above and
below the internuclear axis
– Usually occurs when there is side to side or two parallel p-orbitals
overlap
– Allows for double and triple bonds to form
– There is less overlap area in a pi (π) bond than there is in a sigma
(σ) bond so pi (π) bonds are weaker
 Single Bonds
• 1 σ bond; 0 π bond
• Ex: C2H6
 Double Bonds
• 1 σ bond; 1 π bond
• Ex: C2H4
 Triple Bonds
• 1 σ bond; 2 π bonds
• Ex: C2H2
 Practice Problem
1. Describe how the bonds in formaldehyde, H2CO,
are formed in terms of overlaps of appropriate
hybridized and un-hybridized orbitals.
 Practice Problem
1. Consider the acetonitrile molecule, CH3CΞN
a. Predict the bond angles around each carbon atom
left carbon = 109.5∘ bond angles and the right carbon =180∘ bond angles.

b. Describe the hybridization at each of the carbon atoms

left carbon is sp3 hybridized, i.e. it uses one s orbital and three p orbitals to form
four sp3 hybrid orbitals.

right carbon is sp hybridized, i.e. it uses one s orbital and one p orbital to form two sp hybrid
orbitals.
c. Determine the total number of σ and π bonds in the molecule
• https://socratic.org/questions/596e2824b72cff2edb24d0c5
5 sigma bonds and 2 pi bonds
a bond = 1 sigma bond (& 0 pi bonds)
triple bond = 1 sigma bond and 2 pi bonds

ꭉ ꭉ
ꭉ ꭉ
ꭉ 2π
3. How many sigma and pi bonds?

2π
ꭉ ꭉ ꭉ ꭉ
ꭉ ꭉ ꭉ
ꭉ ꭉ

9 sigma bonds and 1 pi bonds

a single bond = 1 sigma bond (0 pi bonds)
Double bond = 1 sigma bond and 1 pi bond
 Structures with Resonance
• Sigma bonds are localized within the molecule (bonding e- shared
between 2 atoms)
• Pi bonds are delocalized within the molecule (electrons spread over a
number ofR atoms in a molecule not localized on a single atom)
Example: Benzene Ring, C6H6
• Shape of each carbon atom is trigonal planar, 120˚
• Orbitals of carbon hybridize as sp2
• 6 localize C-C bonds; 6 localized C-H bonds
• 6 e- are left for pi bonding… delocalized Resonance structures = delocalized bonding
Because electron move around
 Benzene Ring, C6H6
12 sigma bonds are stationary (localized)
3 pi bonds are resonating (delocalized)
 Practice Problems
1. How many sigma & pi bonds does nitrate (NO3-1) have? Does this
ion have delocalized π bonds?

In reality each of the four atoms in the

nitrate ion has a p orbital

The p orbitals on all three oxygen overlap

with the p orbital on the central nitrogen.

This mean the pi electron are NOT

localized between the nitrogen and on of
the oxygens but are delocalized throughout
the ion
 Practice Problems
1. Which of the following molecules or ions will exhibit delocalized pi
bonding: SO3, SO32-, H2CO, O3, NH4+?
SO3, SO3 2- and O3 are all resonance and therefore show delocalized pi bonding
 Strengths of Covalent Bonds
• The stability of a molecule is related to the strengths of the
covalent bonds it contains

• The strength of the covalent bond between two atoms is

determined by the energy required to break that bond…
aka… the enthalpy change!

• Bond enthalpy, H, is the energy required to break a particular

bond in 1-mol of a gaseous substance

• Bond enthalpy is sometimes referred to as dissociation energy

(energy of bond breaking)… D(bond)
• Example: Cl2(g)  2Cl(g) D(Cl-Cl) = 242 kJ/mol
 Bond Energies
• Table 8.4 (pg 372) lists several avg.
bond enthalpies

• Bond enthalpy is always written as

a (+) quantity
– Energy is always required to
break a bond (endo)
– Energy is always released when
bonds form (exo)

• The greater the bond enthalpy the

stronger the bond!
– Molecules with stronger bonds
are less likely to react
 Bond Enthalpy & Bond Length

• Bond Length
– Single > double > triple

• Bond Enthalpy
– Single < double < triple

# bonds bond enthalpy bond length

• Single bonds are longer & weaker

• Triple bonds are shorter & stronger
 Calculating Bond Enthalpies &
the Enthalpies of Reactions
Hrxn = (nDbroken) – (nDformed)

Hrxn = (bond enthalpies of bonds broken) – (bond enthalpies of bonds formed)

Example: Calculate the Hrxn for H—CH3(g) + Cl2(g)  Cl—CH3(g) + HCl(g)

Bonds Broken: 1 mol C—H, 1 mol Cl—Cl Bonds Formed: 1 mol C—Cl, 1 mol H—Cl

Hrxn = (413 kJ + 239 kJ) – (339 kJ + 427 kJ) = -114 kJ

Hrxn = exothermic; the bonds of the products are stronger than that of the reactants

• Compare this to the value of Hrxn obtained by Hess’s Law (-100 kJ) and you can see that
you are close (reasonable estimate) but since the bond enthalpies are averages you will
not be exact.
 Calculating Bond Enthalpies &
the Enthalpies of Reactions
Things to remember…
1. You must draw the Lewis structure to know if the bonds
are single, double, triple

2. You only need to include the bonds that are changing… so

analyze the bonds first

3. The bond enthalpies given in the table are for 1-mole of

bonds breaking
– If there is more than one mole of bonds being broken or
formed you must multiply the bond energy by the
coefficients
Calculate ΔH for the following reactions:

1. CH4(g) + 2Cl2(g) + 2F2(g)  CF2Cl2(g) + 2HF(g) + 2HCl(g)

Bonds broken: 4C—H, 2Cl—Cl, 2F—F

Bonds broken: [4(413) + 2(239) + 2(154)] = 2438

Bonds formed: 2C—Cl, 2C—F, 2H—F, 2H—Cl

Bonds formed: [2(339) + 2(485) + 2(565) + 2(427)] = 3632

ΔHrxn = Bonds Broken – Bonds Formed

ΔHrxn = 2438 – 3632 = -1194 kJ/mol

exothermic; products have stronger bonds

Calculate ΔH for the following reactions:

2. CH3NC(g)  CH3CN(g)

Bonds broken: 1C—N = 305

Bonds formed: 1C—C = 347

ΔHrxn = Bonds Broken – Bonds Formed

ΔHrxn = 305 – 347 = -42 kJ/mol exothermic

Calculate ΔH for the following reactions:

3. H2(g) + Cl2(g)  2HCl(g)

Bonds broken: 1H—H, 1Cl—Cl

Bonds broken: [432 + 239] = 671

Bonds formed: 2H—Cl

Bonds formed: [2(427)] = 858

ΔHrxn = Bonds Broken – Bonds Formed

ΔHrxn = 671 – 858 = -183 kJ/mol exothermic

Calculate ΔH for the following reactions:

4. N2(g) + 3H2(g)  2NH3(g)

Bonds broken: 1NΞN, 3H—H

Bonds broken: [941 + 3(432)] = 2237

Bonds formed: 6N—H

Bonds formed: [6(391)] = 2346

ΔHrxn = Bonds Broken – Bonds Formed

ΔHrxn = 2237 – 2346 = -109 kJ/mol exothermic

Calculate ΔH for the following reactions:

5. 4CH2=CHCH3 (g) + 6NO(g)  4CH2=CHCN(g) + 6H2O(g) + N2 (g)

Bonds broken: 12C—H, 6N=O

Bonds broken: [12(413) + 6(607)] = 8598

Bonds formed: 4CΞN, 12H—O, 1NΞN

Bonds formed: [4(891) + 12(467) + 1(941)] = 10109

ΔHrxn = Bonds Broken – Bonds Formed

ΔHrxn = 8598 – 10109 = -1511 kJ/mol exothermic