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Chapter 6

Valence electrons are the outer shell electrons of an atom. The valence electrons are the electrons that participate in chemical bonding.
Group 1A 2A 3A 4A 5A 6A 7A e- configuration ns1 ns2 ns2np1 ns2np2 ns2np3 ns2np4 ns2np5 # of valence e1 2 3 4 5 6 7

Lewis Dot Symbols for the Representative Elements & Noble Gases
Lewis dot symbol consists of the symbol of an element and one dot for each valence electron in an atom of the element.

The Ionic Bond

Ionic bond: the electrostatic force that holds ions together in an ionic compound. Atoms of the elements with low ionization energies tend to form cation alkali metals and alkaline earth metals Atoms of the elements with high electron affinities tend to form anion halogens and oxygen Li + F Li+ F -


1s22s1 1s22s22p5 1s2 1s22s22p6

Li e- + Li+ + F F -

Li+ + eF Li+ F -

A covalent bond is a chemical bond in which two or more electrons are shared by two atoms. Why should two atoms share electrons? F 7e+ F 7eF F 8e- 8e-

Lewis structure of F2
single covalent bond lone pairs

lone pairs

lone pairs


lone pairs

single covalent bond

A Lewis structure: - a representation of covalent bonding in which shared electron pairs are shown either as lines or as pairs of dots between two atoms, and lone pairs are shown as pairs of dots an individual atoms. Only valence electrons are shown. The formation of the molecules illustrates the octet rule. - Octet rule: An atom other than hydrogen tends to form bonds until it is surrounded by eight valence electrons.

Lewis structure of water H + O + H H O H 2e-8e-2e-

single covalent bonds


Double bond two atoms share two pairs of electrons O C O

double bonds


8e- 8e- 8e-

double bonds

Triple bond two atoms share three pairs of electrons N N 8e-8etriple bond


triple bond

Lengths of Covalent Bonds

Bond Lengths Triple bond < Double Bond < Single Bond


IONIC COMPOUND Solid at room temperature, high melting points Soluble in water Aqueous solution conduct electricity Strong electrolytes

COVALENT COMPOUND Gases, liquids, low melting solids Insoluble in water Aqueous solution do not conduct electricity Nonelectrolytes

Writing Lewis Structures

1. Count total number of valence e-. Add 1 for each negative charge. Subtract 1 for each positive charge. 2. Draw skeletal structure of compound showing what atoms are bonded to each other. Put least electronegative element in the center. 3. Complete an octet for all atoms except hydrogen 4. If structure contains too many electrons, form double and triple bonds on central atom as needed.

Write the Lewis structure of nitrogen trifluoride (NF 3).

Step 1 N is less electronegative than F, put N in center Step 2 Count valence electrons N - 5 (2s22p3) and F - 7 (2s22p5) 5 + (3 x 7) = 26 valence electrons Step 3 Draw single bonds between N and F atoms and complete octets on N and F atoms. Step 4 - Check, are # of e- in structure equal to number of valence e- ? 3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons


Write the Lewis structure of the carbonate ion (CO 32-).

Step 1 C is less electronegative than O, put C in center Step 2 Count valence electrons C - 4 (2s22p2) and O - 6 (2s22p4) -2 charge 2e4 + (3 x 6) + 2 = 24 valence electrons Step 3 Draw single bonds between C and O atoms and complete octet on C and O atoms. Step 4 - Check, are # of e- in structure equal to number of valence e- ? 3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons Step 5 - Too many electrons, form double bond and re-check # of e 2 single bonds (2x2) = 4 1 double bond = 4 8 lone pairs (8x2) = 16 Total = 24


Write the Lewis structure for: i) NO -2 ii) CS2 iii) SO3

An atoms formal charge is the difference between the number of valence electrons in an isolated atom and the number of electrons assigned to that atom in a Lewis structure.
formal charge on an atom in a Lewis structure total number of valence electrons in the free atom total number electron assigned to atom

The sum of the formal charges of the atoms in a molecule or ion must equal the charge on the molecule or ion.

formal charge on C formal charge on O

= -1 =+1


formal charge on C formal charge on O

=0 =0

Formal Charge and Lewis Structures

1. For neutral molecules, a Lewis structure in which there are no formal charges is preferable to one in which formal charges are present. 2. Lewis structures with large formal charges are less plausible than those with small formal charges. 3. Among Lewis structures having similar distributions of formal charges, the most plausible structure is the one in which negative formal charges are placed on the more electronegative atoms.

Which is the most likely Lewis structure for CH2O? -1 H C +1 O H H H 0 C 0 O

Resonance Structure
A resonance structure is one of two or more Lewis structures for a single molecule that cannot be represented accurately by only one Lewis structure.

What are the resonance structures of the carbonate (CO32-) ion?


C O -

C O -

Exceptions to the Octet Rule

The Incomplete Octet Be 2e2H 2x1e4e-




B 3e3F 3x7e24e-


3 single bonds (3x2) = 6 9 lone pairs (9x2) = 18 Total = 24

Exceptions to the Octet Rule

Odd-Electron Molecules N 5eO 6e11e-


The Expanded Octet (central atom with principal quantum number n > 2) F S F F F


S 6e6F 42e48e-

6 single bonds (6x2) = 12 18 lone pairs (18x2) = 36 Total = 48

Dative Covalent Bond / Coordinate Covalent Bond

A covalent bond in which one of the atoms donates both electrons. Examples: - NH4+, NH3AlCl3, NH3BF3

Hybridization mixing of two or more atomic orbitals to form a new set of hybrid orbitals. 1. Mix at least 2 nonequivalent atomic orbitals (e.g. s and p). Hybrid orbitals have very different shape from original atomic orbitals. 2. Number of hybrid orbitals is equal to number of pure atomic orbitals used in the hybridization process. 3. Covalent bonds are formed by: a. Overlap of hybrid orbitals with atomic orbitals b. Overlap of hybrid orbitals with other hybrid orbitals

Formation of sp3 Hybrid Orbitals

Formation of Covalent Bonds in CH4

sp3-Hybridized N Atom in NH3

Formation of sp Hybrid Orbitals

Formation of sp2 Hybrid Orbitals

How to predict the hybridization of the central atom? 1. Draw the Lewis structure of the molecule. 2. Count the number of lone pairs AND the number of atoms bonded to the central atom # of Lone Pairs + # of Bonded Atoms 2 3 4 5 6

Hybridization sp sp2 sp3 sp3d sp3d2

Examples BeCl2 BF3 CH4, NH3, H2O PCl5 SF6

Bonding in Ethylene, C2H4

Sigma bond () covalent bonds formed by orbitals overlapping end to-end , with the electron density between the nuclei of the bonding atoms Pi bond () a covalent bond formed by sideways overlapping orbitals with electron density concentrated above and below plane of nuclei of the bonding atoms

Another View of Bonding in Ethylene, C2H4

Bonding in Acetylene, C2H2

Describe the bonding in CH2O


C 3 bonded atoms, 0 lone pairs C sp2

Sigma (s) and Pi Bonds (p)

Single bond Double bond Triple bond 1 sigma bond 1 sigma bond and 1 pi bond 1 sigma bond and 2 pi bonds

How many and bonds are in the acetic acid (vinegar) molecule CH3COOH? H H C H

C O H bonds = 6 + 1 = 7 bonds = 1

Intermolecular Forces
Intermolecular forces: attractive forces between molecules. Van der Waals forces: - the attractive or repulsive force between molecules due to covalent bonds or to the electrostatic interaction of ions with one another or with neutral molecules. The term includes: - permanent dipolepermanent dipole forces - instantaneous induced dipole-induced dipole (London dispersion force). Examples: interaction between H2, Cl2, F2, CH4

Hydrogen Bond
The hydrogen bond is a special dipole-dipole interaction between they hydrogen atom in a polar N-H, O-H, or F-H bond and an electronegative O, N, or F atom. A HB or A HA

A & B are N, O, or F

Why is the hydrogen bond considered a special dipole-dipole interaction?

Decreasing molar mass Decreasing boiling point