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10-1
Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Chapter 3
Chemical Bonding
10-2
Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Chemical Bonding
How do atoms combine to form compounds? How do atoms react in chemical reactions? These questions are fundamental to chemistry since chemical changes are essentially alterations of chemical bonds.
CHEMICAL BOND – the force that holds atoms together to from ionic or molecular compound.
G.N. LEWIS (1916)
“Atoms interact to gain stability by changing the outermost (valence) configuration so as to attain the electronic configuration of a noble gas.”
10-3
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Lewis Theory
1. Valence electrons play a fundamental role in chemical bonding.
2. Chemical bonding may result from: *transfer of one/more electrons ionic bond *sharing of electrons between atoms covalent bond
3. Electrons are transferred or shared until each atom acquires an OCTET of outer shell (valence) electrons OCTET RULE
10-4
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Lewis Dot Symbol
– shows valence electrons; symbols of the elements surrounded by dot to represent the valence electrons.
*for main group elements group # = # valence electrons
10-5
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Octet Rule
– the tendency to achieve an electronic configuration with eight valence electrons. An octet of electrons consists of a full s and p subshells of an atom.
Lewis Structures – a combination of Lewis symbols representing the transfer or sharing of electrons in a chemical bond.
10-6
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Types of Bonding
1. Ionic Bonding
- involves complete transfer of electrons- usually metallic and nonmetallic elements are involved- metals lose electrons (cations) and nonmetals gain electrons (anions)
Ex. Na + Cl NaCl
10-7
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2. Covalent Bonding
- sharing of electrons- between nonmetals or between metalloids- leads to formation of molecules (vs ionic compounds)
10-8
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How about if you are asked to write the Lewis Structure of a polyatomic
compound?
10-9
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Rules for Writing Lewis Structures
1. Count the total number of valence electrons present – from atoms– from charge if polyatomic ion (add or subtract e–s for
charge)
2. Write the skeleton structure of the compound – The atom with the least number will be the central atom – Put least EN atom as central atom and surround with
other atoms – Note: H and F atoms will always be outer atoms
3. Connect all atoms by drawing single bonds between all atoms, then distribute the remaining valence electrons as lone pairs around outer atoms so each has 8 electrons
octet rule: atoms form bonds such that all atoms get eight electrons
10-10
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4. If there are not enough electrons for each atom to have an octet, make double and/or triple bonds between central atom and surrounding atoms
– BUT fluorine can only form a single bond – Note that double bonds are shorter than single
bonds, and triple bonds are shorter than double bonds
5. For polyatomic ions, square brackets are drawn around the Lewis structure, and the charge is put in the upper right-hand corner
10-11
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Figure 10.1The steps in converting a molecular formula into a Lewis structure.
Molecular formula
Atom placement
Sum of valence
e-
Remaining valence
e-
Lewis structure
Place atom with lowest EN in center
Add A-group numbers
Draw single bonds. Subtract 2e- for each bond.
Give each atom 8e-
(2e- for H)
Step 1
Step 2
Step 3
Step 4
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Examples:
1.CCl4
2.NF3
3.NH4+
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Molecular formula
Atom placement
Sum of valence e-
Remaining valence e-
Lewis structure
For NF3
NFF
F
N 5e-
F 7e- X 3 = 21e-
Total 26e-
:
: :
::
: :
:: :
10-14
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SAMPLE PROBLEM 10.1 Writing Lewis Structures for Molecules with One Central Atom
SOLUTION:
PROBLEM: Write a Lewis structure for CCl2F2, one of the compounds responsible for the depletion of stratospheric ozone.
PLAN: Follow the steps outlined in Figure 10.1 .
Step 1: Carbon has the lowest EN and is the central atom.
The other atoms are placed around it.
C
Steps 2-4: C has 4 valence e-, Cl and F each have 7. The
sum is 4 + 4(7) = 32 valence e-.
Cl
Cl F
F
C
Cl
Cl F
FMake bonds and fill in remaining valence
electrons placing 8e- around each atom.
:
::
::
:
:
::
: ::
10-15
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SAMPLE PROBLEM 10.2 Writing Lewis Structure for Molecules with More than One Central Atom
PROBLEM: Write the Lewis structure for methanol (molecular formula CH4O), an important industrial alcohol that is being used as a gasoline alternative in car engines.
SOLUTION: Hydrogen can have only one bond so C and O must be next to each other with H filling in the bonds.
There are 4(1) + 4 + 6 = 14 valence e-.
C has 4 bonds and O has 2. O has 2 pair of nonbonding e-.
C O H
H
H
H
::
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SAMPLE PROBLEM 10.3 Writing Lewis Structures for Molecules with Multiple Bonds.
PLAN:
SOLUTION:
PROBLEM: Write Lewis structures for the following:
(a) Ethylene (C2H4), the most important reactant in the manufacture of polymers
(b) Nitrogen (N2), the most abundant atmospheric gas
For molecules with multiple bonds, there is a Step 5 which follows the other steps in Lewis structure construction. If a central atom does not have 8e-, an octet, then two e- (either single or nonbonded pair)can be moved in to form a multiple bond.
(a) There are 2(4) + 4(1) = 12 valence e-. H can have only one bond per atom.
CCH
H H
H
:
CCH
H H
H
(b) N2 has 2(5) = 10 valence e-. Therefore a triple bond is required to make the octet around each N.
N
:
N
:
. .
..
N
:
N
:
. . N
:
N
:
10-17
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Exceptions to the Octet Rule
1. s2 group2. molecules with odd number of electrons; e.g. NO, NO23.molecules with less than an octet: atoms that participate in bonding but do not have enough valence e-s to form an octet. e.g. BF34. molecules with more than an octet: atoms in periods 3 to 7 with expanded d valence shells. e.g. PCl5, SiF62-, POl3, SF6*Since the second-period elements only have 2s and 2p valence orbitals available for bonding, and these orbitals can hold a maximum of eight electrons, the second-period elements can never have more than an octet of electrons.*Elements in the 3rd to 7th period have unfilled nd orbitals that can be used in bondingIllustration: Draw the orbital diagram for period 3 elements.
10-18
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SAMPLE PROBLEM 10.5 Writing Lewis Structures for Octet Rule Exceptions
PLAN:
SOLUTION:
PROBLEM: Write Lewis structures for BFCl2.
Draw the Lewis structures for the molecule and determine if there is an element which can be an exception to the octet rule.
BFCl2 will have only 1 Lewis structure.
F
BCl Cl
10-19
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Formal Charge: Selecting the Best Resonance Structure
An atom “owns” all of its nonbonding electrons and half of its bonding electrons.
Formal charge of atom =
# valence e- - # of covalent bonds - # of nonbonding electrons
OO O
A
B
C
For OA
# valence e- = 6
# nonbonding e- = 4
# bonding e- = 4 X 1/2 = 2
Formal charge = 0
For OB
# valence e- = 6
# nonbonding e- = 2
# bonding e- = 6 X 1/2 = 3
Formal charge = +1
For OC
# valence e- = 6
# nonbonding e- = 6
# bonding e- = 2 X 1/2 = 1
Formal charge = -1
The smaller the formal charge of the atoms, the more stable the structure
10-20
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Theories of Covalent Bonding
10-21
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Valence Bond Theory
Hybridization Theory
Valence Shell Electron Pair Repulsion Theory
Molecular Orbital Theory
10-22
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The Central Themes of VB Theory
Basic Principle
A covalent bond forms when the orbitals of two atoms overlap and the overlap region, which is between the nuclei, is occupied by a pair of electrons.
The two wave functions are in phase so the amplitude increasesbetween the nuclei.
10-23
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The Central Themes of VB Theory
Themes
A set of overlapping orbitals has a maximum of two electrons that must have opposite spins.
The greater the orbital overlap, the stronger (more stable) the bond.
The valence atomic orbitals in a molecule are different from those in isolated atoms.
There is a hybridization of atomic orbitals to form molecularorbitals.
10-24
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Figure 11.1 Orbital overlap and spin pairing in three diatomic molecules.
Hydrogen, H2
Hydrogen fluoride, HF
Fluorine, F2
10-25
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Hybridization Theory
Basic Principle
the process of mixing of atomic orbitals of the same atom to form degenerate orbitals called hybrid orbitals
- the number of hybrid orbitals formed is equal to the number of pure atomic orbitals that combine.
10-26
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Hybrid Orbitals
The number of hybrid orbitals obtained equals the number of atomic orbitals mixed.
The type of hybrid orbitals obtained varies with the types of atomic orbitals mixed.
Key Points
sp sp2 sp3 sp3d sp3d2
Types of Hybrid Orbitals
10-27
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Figure 11.2 The sp hybrid orbitals in gaseous BeCl2.
atomic orbitals
hybrid orbitals
orbital box diagrams
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Figure 11.2 The sp hybrid orbitals in gaseous BeCl2(continued).
orbital box diagrams with orbital contours
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Figure 11.3 The sp2 hybrid orbitals in BF3.
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Figure 11.4 The sp3 hybrid orbitals in CH4.
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Figure 11.5 The sp3 hybrid orbitals in NH3.
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Figure 11.5 continued The sp3 hybrid orbitals in H2O.
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Figure 11.6 The sp3d hybrid orbitals in PCl5.
10-34
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Figure 11.7 The sp3d2 hybrid orbitals in SF6.
10-35
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Figure 11.8
Shortcut in getting the hybridization of the central atom:
Molecular formula
Lewis structure
Count no. of atoms attached and lone pairs
hybridization
Figure 10.1
Step 1
Figure 10.12
Step 2 Step 3
Table 11.1
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Number of atoms attached + Lone Pairs
Hybrid Orbitals
2 sp
3 sp2
4 sp3
5 sp3d
6 sp3d2
10-37
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sp3 hybridized
Hybridization of the central atom:
No. of lone pairs = 1
No. of atoms attached = 3
Lewis structure
1.NF3
NFF
F
:
: :
::
: :
:: :
10-38
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sp2 hybridized
Hybridization of the central atom:
No. of lone pairs = 1
No. of atoms attached = 2
Lewis structure
2. O3
OO O
10-39
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sp3d hybridized
Hybridization of the central atom:
No. of lone pairs = 1
No. of atoms attached = 4
Lewis structure
3. SF4
SFF
F
F
10-40
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What are the hybrid orbitals for the central atom in each of the following molecules?a. PCl3 d. IBr4–:b. NH2– e.SCN–c. SeF4 f. SnCl5–