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Bonding
a chemical bond forms when the potential
energy of the bonded atoms is less than the
potential energy of the separate atoms
consider following interactions:
nucleus-to-nucleus repulsion
electron-to-electron repulsion
nucleus-to-electron attraction
4 0 r
0 is a constant
Bonding theories
bond lengths
bond angles
magnetic properties
bond dissociation energies
spectra
easier to design experiments with a predicted structure in hand
Bonding theories
Lewis Theory
Valence-bond Theory
Si
Al
As
Se
Bi
Sb
Ar
[ I ]
Al3+
Practice Example:
Draw Lewis Structures for the following atoms and ions:
C
ClNe
O2-
Cl
B3+
Ca
Li
Ca2+
EXAMPLE 10-2
Writing Lewis Structures of Ionic Compounds. Write Lewis
structures for the following compounds: (a) BaO; (b) MgCl2 ;
(c) aluminum oxide.
O
2+
Ba [ O ]
2-
Ba
BaO
Ionic Compounds
Mg
Cl
2[ Cl ]
2+
Mg
MgCl2
Cl
Practice Examples:
Draw Lewis Structures of the following compounds
HF
CH4
CaO
CLICKER QUESTION
O C O
O C O
O C O
N N
N N
N N
Cl
H N H
Cl
H N
2.
3.
4.
5.
6.
H O H
3.
HOH
4.
5.
Add lone pairs to outer atoms none in this case for H atoms
Place remaining electrons on central atom
HOH
Add up electrons to check
NOTE: Can also draw lines for bonds; one line represents one pair of
electrons:
O
Example 2: CS2
1. Find the total number of valence electrons:
C 4 ; S 6; S 6; total =16
2. Choose the central and terminal atoms
S C
S
3. Draw atoms with pairs connecting
S:C:S
4. Add lone pairs to the outer atoms (except H) to give complete octet
S C S
5. Place all remaining electrons in lone pairs on the central atom (no
electrons left)
6. If an octet does not form on the central atom, draw multiple bonds
between central and outside atoms
OR
S C S
S C S
S C S
Practice Example:
Draw Lewis structures for the following molecules:
PCl3
CH3Cl
CN-
Formal Charge
When more than one Lewis structure is feasible, formal charges can
be used to choose the correct structure
Example: CS2
FC (C) = 4-0-4 = 0
FC (S) = 6-4-2 = 0
Formal Charge
S C S
FC (C) = 4-0-4 = 0
FC (Sl) = 6-6-1 = -1
FC (Sr) = 6-2-3 = +1
EXAMPLE 10-7
Using the Formal Charge in Writing Lewis Structures. Write
the most plausible Lewis structure of nitrosyl chloride, NOCl,
one of the oxidizing agents present in aqua regia.
2+
2-
2+
Practice Example:
Resonance
When two or more Lewis structures are equally feasible, but none
represents the true structure
Resonance hybrid
The correct structure is considered an weighted average of the
resonance structures (NOTE: the different resonance structures may
or may not contribute equally to the average)
Resonance structures of O3
- +
+ -
O
O O
O
O O
Resonance hybrid of O3
+ -
O
O O
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 391
Practice Example
Draw resonance structures for the SO2 molecule
CLICKER QUESTION
Odd-Electron Species
Radicals
Incomplete Octets
Boron, Hydrogen
Period 3 and up
Odd-Electron Species
Species that contain unpaired electrons are called radicals
HCH
or
CH3
Incomplete Octets
Some species do not have an electron deficiency and cannot complete
their octets
Boron has only three electrons to share and has a very low
electronegativity
Expanded Octets
Some atoms can have up to 12 electrons surrounding them. They
usually involve larger atoms (period 3 and up)
Examples:
Cl
Cl
F
S
Cl
Cl
Cl
Practice Example:
Draw Lewis structures for the following molecules:
AsF5
BCl3
SF5-
CLICKER QUESTION
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 382
Cl
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 380
Practice Example:
Determine which of the following bonds are polar. Classify each
as non-polar covalent, polar covalent, or ionic in character. Use
the cross-based arrow symbol for the polar covalent bonds.
H-Br
N-H
P-Cl
C-H
Shapes of Molecules
Lewis structures show the atom-to-atom connections in a molecule,
but they do not necessarily show the correct three-dimensional
shape of a molecule
Example: H2O
Lewis structure of H2O
HOH
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 395
Electronic geometry
The geometric shape that electron clouds form around the central
atom such that they are as far apart as possible. Lone pairs and
bonds count as electron clouds
180o
Practice: Build model of linear geometry. Use brown or silver center atom.
Electronic geometry
120o
Electronic geometry
109.5o
180o
120o
Electronic geometry
180
Molecular geometry
The geometric shape that outer atoms form around the central atom
(lone pairs are NOT included)
Chemistry: A Molecular Approach, Tro 1st edition, 2008, Pearson Prentice Hall, p. 411
Shapes of Molecules
Example: H2O
O H
O
H
H
Practice Examples:
Determine the electronic and molecular geometries of the
following molecules:
PCl3
AsF5
SF5-
CLICKER QUESTION
Cl
Vector addition
.
Chemistry: A Molecular Approach, Tro 1st edition, 2008, Pearson Prentice Hall, p. 420
2.
Difference in electronegativity;
1.4 = (3.5-2.1)
Mark the bonds with cross-based arrows
O
H
The molecule H2O is polar. The net polarity is toward the oxygen.
Chemistry: A Molecular
Approach, Tro 1st edition,
2008, Pearson Prentice
Hall, p. 419
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Madura, Bissonnette 10th ed., 2011, Pearson Prentice Hall, p. 432
Practice Examples:
Determine which of the following molecules are polar:
PCl3
AsF5
CLICKER QUESTION
Bond Order
indicates the number of shared electron pairs in a bond
Bond Length
the distance between the centers of the two atoms joined by a
covalent bond
bond length decreases with increasing bond order
you can approximate the bond length by averaging the covalent
radii of the two atoms joined by the covalent bond (use single
bonds only)
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 347,
407
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 407
Bond broken
435.93 kJ/mol
H2 (g)
H (g) + H (g)
Bond formed
DH = 435.93 kJ
H (g) + H (g)
435.93 kJ/mol
H2 (g)
DH = -435.93 kJ
Chemistry: A Molecular Approach, Tro, 1st edition, 2008, Pearson Prentice Hall, p. 393
In effect, we need to break two H-H bonds and one O-O bond and form
four O-H bonds.
This gives: 2x(+436 kJ) + 498 kJ +4x(-464 kJ) = -486 kJ
Bond Energies
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 409
Practice Example:
What is the bond order of the nitrogen-to-hydrogen bonds in
NH3?
Estimate the bond lengths in the molecule NH3