Structure and Bonding Fundamental Concepts

Table of Contents
Chapter 9: Structure and Bonding Fundamental Concepts...........................2
Structure .........................................................................................................................................2
Bonding ..........................................................................................................................................2

Bonding Types..........................................................................................................................3
Ionic Bond.........................................................................................................................................3
Covalent Bond...................................................................................................................................3

Electronegativity......................................................................................................................3
Bonding - Ionic Bonds.............................................................................................................4
Why do ionic bonds form?.................................................................................................................4
Crystalline Substances.......................................................................................................................5

Covalent Bonding.....................................................................................................................8
Electron Dot Structures (a.k.a. Lewis Dot Structures).......................................................................8
Lewis Dot Structures For Ions...........................................................................................................9
Lewis Dot structures for Molecules.................................................................................................10

Resonance Structures............................................................................................................14
Features of Resonance.....................................................................................................................15
Bond Order......................................................................................................................................16

Formal Charge.......................................................................................................................17
Definition:.......................................................................................................................................17
Counting Rules................................................................................................................................17
Electroneutrality Principle..............................................................................................................18
Formal Charge Examples................................................................................................................18

VSEPR Theory.......................................................................................................................20
Valence Shell Electron Pair Repulsion Theory................................................................................20
VSEPR Geometries..........................................................................................................................21
VSEPR for Multiple central Atoms..................................................................................................26

Molecular Polarities...............................................................................................................27
Dipole Moment .............................................................................................................................28

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Structure and Bonding Fundamental Concepts

Chapter 9: Structure and Bonding Fundamental Concepts

Structure
Bonding

A Bond:
These are both determined based on arrangements of electrons.
Electrons are subdivided into 2 categories:
1. Core Electrons

2. Valence Electrons

For main group elements, the number of valence electrons is

equal to
(The sum of the _________ electrons)
Na
K
Rb
F
Cl
Br
Bonding Types
The attractive forces that hold atoms together to form a chemical
bond come in 2 general types:

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Structure and Bonding Fundamental Concepts

Ionic Bond

One or more valence e-s are

Covalent Bond

All covalently bonded atoms _____________

Non-polar covalent bonds _______________________________
Polar covalent bonds___________________________________

Picture form http://www.avonchemistry.com/chem_bond_explain.html

Electronegativity
Is:
It is a continuum.
Electronegativity follows the general trends of
EN < 0.4
EN 0.5-1.6
EN >1.6 (some say 2)
(metal plus nonmetal:

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Structure and Bonding Fundamental Concepts

____ is the most

electronegative (4.0)
Chart of electronegativities form
http://www.avonchemistry.com/chem_bond_explain.html

Bonding - Ionic Bonds

Why do ionic bonds form?

Na has a low
Cl has a high
You would expect that the formation of NaCl would be
thermodynamically favored (which it is). H =
HOWEVER, the change in energy upon formation of a salt cannot be
accounted for just by the ___ for the cation + the ___ for the anion.
I.E. for
E.A. for

Cl(g)

This would predict that energy is needed, but the Rxn is spontaneous.
The difference is the stability coming from the electrostatic
attractive forces.
The attractive force is governed by _____________________
Where e is the charge on an en+ is the charge on the (+) ion
n- is the charge on the (-) ion
d = distance between them
C = a constant
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Structure and Bonding Fundamental Concepts

This means:
Higher charges have _________________
Larger ions have _______ distances between the (+) and (-)
charges leading to
For NaCl in the gas phase, the

ion pair energy

is 498 kJ/mol

Crystalline Substances

So far we have assumed that all substances are in the gas phase because
that is the way that ionization energy and electron affinity are defined.

Picture from McMurry Fay 3rd Ed.

Lattice Energy:
Na+(g) + Cl-(g)

picture from http://www.le.ac.uk/eg/spg3/NaCl.gif

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Structure and Bonding Fundamental Concepts

Lattice E for NaCl:

Additional Stabilization
Additional energy for the overall cycle is required to calculate the net
energy for the formation of NaCl from room temperature reactants:
You need to get atoms of Cl in the gas phase (break Cl-Cl bond)

You need to have Na in the gas phase (vaporize Na)

The complete cycle is called a Born-Haber Cycle

The Born-Haber Cycle for Sodium Chloride. Picture from McMurry Fay 3
Page 6 of 30

rd

Ed.

Structure and Bonding Fundamental Concepts

Picture from
McMurry Fay 3rd
Ed.

If time Permits, work out Born-Haber Cycle for MgCl2

Example:
What is the E for the formation of magnesium chloride from
magnesium metal and chlorine gas given the following information:
The lattice energy for magnesium chloride is 2542 kJ/mol
The first ionization energy for magnesium is 737.7 kJ/mol
The second ionization energy for magnesium is 1450.7 kJ/mol
The electron affinity for chlorine is -384.6 kJ/mol (x2 = -697.2 kJ/mol)
The H of formation (sublimation) of Mg(g) is 147.7 kJ/mol
The Cl-Cl bond energy is 243 kJ/mol

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Structure and Bonding Fundamental Concepts

Covalent Bonding
Typically takes place when ____________
Typical between ______________
Involves __________________
Electron Dot Structures (a.k.a. Lewis Dot Structures)

These are a way of representing the number of electrons surrounding or

shared by each _________________________
These are cartoons, _______________________.
These were invented by
Theory proposed in 1916
Lewis dot structures are only relevant for ___________________
Start with ________________________
representing the inner electrons
Indicate atoms valence electrons _______________
on the 4 sides of the symbol.
Remember, units place of the group number indicates
When atoms combine to form molecules
Shared electrons are called ________________
Unshared electrons are called lone electrons or lone pairs
Atoms share as many valence shell electrons as possible (until
there are no more electrons to share or until an ___________
(most stable configuration) is reached.

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Structure and Bonding Fundamental Concepts

Generic Lewis Dot Structures

1

Examples of H plus period 2 nonmetals

(metals dont form covalent bonds)

Lewis Dot Structures For Ions

add or subtract electrons to account of charge

For Ions, include symbol in bracket.

Ex: Sodium metal plus oxygen gas:

2 Na(s) + O2(g) Na2O(s)

Octet Rule: The tendency of molecules or polyatomic ions to have

structures in which eight electrons surround each atom.

Page 9 of 30

Structure and Bonding Fundamental Concepts

Some molecules will _________________

in order to satisfy the octet rule.
Example of a double bond
Example of a triple bond
Two bonding pairs is called a _________________
Three bonding pairs is called a _________________
Lewis Dot structures for Molecules

Rules for Writing Lewis Dot Structures for Molecules

1. Add up valence electrons from all atoms
2. Identify the central and terminal atoms and write the skeletal
structure

H
O
C
3. Draw a bond between each pair of atoms an appropriate.
4. Assign remaining e5. If there are leftover e-,

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Structure and Bonding Fundamental Concepts

6. If all e- are used up and the central atoms do not have completed
octets,
Note: If there is a choice more than one arrangement of electrons will
satisfy the requirements of items 5 and/or 6, choose based on the lowest
formal charge. (We will define formal charge momentarily.)
Examples for Rows 1 + 2 (Octet rule never exceeded) (Boron less
than full octet)
H2O

NH3

CN-

Have class try

N2H4

and

Page 11 of 30

CO2

Structure and Bonding Fundamental Concepts

Exceptions to Octet Rule and Lewis Dot Structures below 2nd Row

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Structure and Bonding Fundamental Concepts

Examples
SeF6

BrF3

Have Class try sulfur tetrafluoride (SF4) and phosphorous

pentachloride (PCl5)

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Structure and Bonding Fundamental Concepts

Resonance Structures
When a molecule is represented by the average of one or more possible
Lewis structures, these are called _______________
(net effect of individual resonance structures)
Example: Ozone O3

4)

Which O atom should move its e- pair?

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Structure and Bonding Fundamental Concepts

Example: Acetate Ion CH3COO-

Which should be the O to move it's electrons?

Features of Resonance

Contributors to a resonance hybrid must all share

Resonance hybrids do NOT _____________________________
(This is a man-made model to try to explain nature.)
Compounds with resonance structures do NOT ______________
The

true

structure

is

____________________________

Bond Order

Bond type

Bond
Order

Length

When resonance structures exist, you can have

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Strength

Structure and Bonding Fundamental Concepts

For ozone O3,

Have class try NO3- ion.
Which O forms double bond?

Bond Order =
For oxyanions,
To form the acid,

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Structure and Bonding Fundamental Concepts

Formal Charge
_______________________________________________________
_______________________________________________________
_______________________________________________________
_______________________________________________________
_______________________________________________________
_______________________________________________________
Definition:

___________________________________________________________
___________________________________________________________
FC = _________________________________________________
OR

FC = _________________________________________________

Each atom in a molecule gets its own formal charge

(like oxidation number is assigned to each atom during redox)
Counting Rules

Lone Pairs - belong entirely to the atom ___

Shared pairs are divided equally
-single bond
-double bond
-triple bond

___
___
___

Essentially, every dot _______________

every line _______________.
The formal charges for all atoms must add up to
______________________ for neutral molecules and
______________________ for ions.

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Structure and Bonding Fundamental Concepts

Electroneutrality Principle

Structures with the __________________________are most stable.

They are not trying to maintain ____________________________.
Compare by adding ________________________of formal charges.
If charges must exist, the negative formal charges should be on
the ________________________________________.
Internal atoms have to _________their electrons and turn out with a
more ____ formal charge.
Formal Charge Examples

Pick the best formula for NOCl

Reject N OCl _______________________________________
_______________________________________
OClN
vs
ONCl
1.
4.

5a1
5a2
Structure
Free atom
5a1
5a2
5b1
5b1

5b1
5b2
Formal Charge Summary
O
Cl
N

Problems with other structures:

________________________________________________________
_________________________________________________________

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Structure and Bonding Fundamental Concepts

What is the best resonance structure for OCN- ?

Assume that the skeleton is OCN.
1
2/3
4
5
6
A

Structure

O (__)

C (__)

N(__)

A
B
C

Page 19 of 30

Structure and Bonding Fundamental Concepts

VSEPR Theory
Valence Shell Electron Pair Repulsion Theory

Pronounced __________
Lewis Dot Structures do NOT imply any ___________.
VSEPR attempts to predict _________ of molecules
based on electrons will try to stay __________________________,
since negative charges will ________________________________
We start by identifying electron ______________.
These include:
_____________________
_____________________
_____________________
(triple, double and single bonds only count as _____ group)
Order of Greatest Repulsion
_____________________
_____________________
_____________________
The actual structure is bases on the ____________ of electron groups
(areas of _____________________)
Like Lewis Dot Structures,
the success of this model is limited to _________________________
The arrangement of electron groups is called the
________________________________.
The arrangement of the atoms is called the
________________________________.

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Structure and Bonding Fundamental Concepts

VSEPR Geometries
All pictures in this section are from McMurry Fay, 3rd ed.

For 2 Electron Groups (density regions/charge clouds):

Bond Angle:
_____________
Electron Pair
Geometry:
_____________
Molecular
Geometry
_____________
For 3 Electron Groups (density regions/charge clouds):
Bond Angle:
_____________
Electron Pair
Geometry:
_____________
Molecular
Geometry
_____________

OR
_____________

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Structure and Bonding Fundamental Concepts

For 4 Electron Groups (density regions/charge clouds):

Bond Angle:
_____________
Electron Pair
Geometry:
_____________
Molecular
Geometry
_____________
OR
_____________
OR
_____________

For 5 Electron Groups (density regions/charge clouds):

Bond Angles:
_____________ (axial) and __________ (equatorial)
Electron Pair
Geometry:
_____________
Molecular
Geometry
_____________
OR

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Structure and Bonding Fundamental Concepts

For 5 Electron Groups (density regions/charge clouds) Continued:

OR
Molecular
Geometry
_____________

OR
_____________

OR
_____________

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Structure and Bonding Fundamental Concepts

For 6 Electron Groups (density regions/charge clouds):

Bond Angle:
_____________
Electron Pair
Geometry:
_____________
Molecular
Geometry
_____________
OR
_____________

OR
_____________

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Structure and Bonding Fundamental Concepts

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Structure and Bonding Fundamental Concepts

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Structure and Bonding Fundamental Concepts

VSEPR for Multiple central Atoms

Ethane

Each bond is______________________ and the C-C bond can

provide
the minimum amount of ______________________.

spin

Ethene (C2H4)

Methyl Isocyanate

Each C is ____________________;
Overall molecule is _____________
Multiple bonds cant ___________ .
Leads to _____________________.

CH3NCO
H
H

N==C==O

Trigonal Planar:
3 Groups

H
Linear:
2 Groups
Tetrahedral:
4 Groups

Page 27 of 30

to

Structure and Bonding Fundamental Concepts

Molecular Polarities
Bond Polarities __________________________________________
If EN is < 0.4, ___________________________________________
If EN is . 0.4, ____________________________________________
Molecular Polarities Based on relationships between all bond
polarities in a molecule.
To Determine Molecular Polarity:
1. _______________________________________________________
2. _______________________________________________________
3. _______________________________________________________
_______________________________________________________
Draw Vectors ___________________________________________
Points toward__________________________________________
If vectors cancel, then the molecule is non-polar.

Dipole Moment

The net sum of the bond vectors. +

Example
NH3 (8 ve)

__ bonds
__ bonds
__ lone pair
Page 28 of 30

__ centers of
electron density

Structure and Bonding Fundamental Concepts

Lewis Structure:

e- geometry is ________________
molecular geometry is _______________

EN = 3.0(N) - 2.1(H) = 0.9

-

N
H

Vectors: ________________
Polarity: ________________

Example
CO2 (16 ve)

__ bonds
__ bonds
__ lone pair

__ centers of
electron density

e- geometry is _______________
molecular geometry is _____________
EN = _________________________
Vectors point _________________________
Vectors ____________Polarity: ________________

Page 29 of 30

Structure and Bonding Fundamental Concepts

Example
Isopropyl alcohol (rubbing alcohol)
(CH3)2CHOH

Page 30 of 30