Chemistry 102 for Eng.

students
Dr. Rasha El-Nashar 8th lecture

Objectives.

Define the term hybridization. Apply different types of orbital hydbridization. Determine effect of Double bonds.

Hybridization

In forming bonds, atomic orbitals overlap to share electrons. There are different types of this overlap to give what is called hybridization. Hybridization, is a modification of the localized electron model to account for the observation that atoms often seem to use special atomic orbitals in forming molecules. The valence orbitals, associated with the highest principal quantum level that contain electrons on a given atom are responsible for hybridization. 3

sp3 hybridization

Consider the structure of methane, For the hydrogen atoms in methane, the valence electrons are present in 1s orbitals while in case of a carbon atom, the valence orbitals are 2s and 2p orbitals. In thinking about how carbon can use these orbitals to bond to the hydrogen: Using the 2p and 2s orbitals will lead to two different types of C-H bonds.
a)

those from the overlap of a 2p orbitals of carbon and a 1s orbitals of hydrogen (3 of these) and b) those from the overlap of a 2s orbitals of carbon and a 1s orbital of hydrogen (one of these). This is a problem because methane is known to have 4 identical C-H bonds. 4

sp3 hybridization (cont.)

Since the carbon 2p orbitals are mutually perpendicular, we might expect that the three C-H bonds formed with these orbitals are oriented at 90 angles (360/3=90). However, the methane molecules is known to be tetrahedral with bond angles 109.5. Either the simple localized electron model is wrong or carbon adopts a set of atomic orbitals other than its native 2s and 2p orbitals to bond to the hydrogen atoms in forming the methane molecule. This conclusion seems more reasonable. This mixing of native orbitals to form special orbitals for bonding is called hybridization
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sp3 hybridization (cont.)

The four new orbitals are called sp3 orbitals because they are formed from one 2s and three 2p orbitals. That is sp3 hybridization. The four orbitals are identical in shape, each one having a large lobe and a small lobe.

2p 2s 1s
promotion

sp3

sp3
C-H bonds

1s
hybrid

1s
Forming bonds
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sp3 hybridization (cont.) H2O molecule

2p

sp3

sp3
lone pairs O-H bonds

Energy

2s 1s
O atom (ground state)

1s
O atom (hybridized state)

1s
O atom (in H2O)
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sp3 hybridization (cont.)

Sp2 hybridization

Consider ethylene, C2H4 molecule: Remember that a double bond acts as one effective pair, so in the ethylene molecule each carbon is surrounded by three effective pairs. This requires a trigonal planar arrangement with bond angles of 120. So we need 3 equivalent orbitals, and again the 2s and 2p are not equivalent. In this molecule, three orbitals are needed and can be obtained from interaction between one 2s and two 2p orbitals giving sp2 hybridization.
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Sp2 hybridization (cont.)

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Notice that, In forming the sp2 orbitals, one 2p orbital on carbon has not been used. This remaining p orbital (pz) is oriented perpendicular to the plane sp2 orbitals.

The three sp2 orbitals on each carbon atom can be used to share electrons. In each of these bonds, the electron pair is shared in an area centered on a line running between the atoms. This type of bonds is called sigma() bonds.

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What about the double bond???

In the bond, the electron pair occupies the space between the carbon atoms. The second bond must therefore result from sharing an electron pair in the space above and below the bond. This type of bond can be formed using the 2p orbital perpendicular to the sp2 hybrid orbitals on each carbon atom. These parallel p orbitals can share an electron pair, which occupies the space above and below the line joining the atoms, to form a pi () bond.

* Note that, bonds are formed from Orbitals whose lobes point towards each other, but bonds result from parallel orbitals.

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sp hybridization

Consider the molecule of carbon dioxide, having the following Lewis structure. ::O=C=O:: In this case, two effective pairs around the carbon atom are required. This is an Sp hybridization involving one s orbital and one p orbital. Note the two 2p orbitals remain unchanged on the sp hybridized carbon. These are used to form the two bonds with the oxygen atom.

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The hybrid orbitals in CO2 molecule can be represented as:

The same type of hybridization can be applied for the N2 molecule with a Lewis structure :NN:, but in this case the 2 unhybridized p orbitals are used to form the triple bond.

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dsp3 hybridization
Consider SF4, PCl5, a set of five effective pairs around the P atom is required.
In general, a set of five effective pairs around a given atom always requires a trigonal bipyramidal arrangement, which in turn requires dsp3 hybridization of that atom

d2sp3 hybridization
Consider SF6, XeF4 (2 lone pairs around Xe).
In general, six electron pairs around an atom are always arranged octahedrally and require d2sp3 hybridization of the atom.
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Hybridization with d-Orbitals, 3rd Row: Extension of Octet Rule p d

Hybridization Bonding

F F F

S 3s23p4

dsp3
trigonal-bipyramidal

F
lone pair

F S F F SF4

d
Hybridization Bonding

F F F F

S 3s23p4

d2sp3 F
S octahedral F F

F F

SF6

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The relationship of the number of effective pairs, and their hybrid orbitals are given in the table

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Example: For each of the following molecules or ions, predict the hybridization of each atom
and describe the molecular structure.

a. CO The Lewis structure is :C O:

Each atom has two effective pairs, which means that both are sp hybridized.

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b. BF4The Lewis structure for such ion is It has four pairs of electrons around The boron atom, which means a tetrahedral structure.

This requires sp3 hybridization of the boron atom

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C. XeF2

*It is not a must that all the atoms have the same type of hybridization

The Lewis structure shows five electron pairs on the xenon atom, which requires a trigonal bipyramidal arrangement.

To accommodate five pairs at the vertices of a trigonal bipyramid requires that the Xenon atom adopt a set of five dsp3 orbitals. Each fluorine atom has four electron pairs and can be assumed to be sp3 hybridized.
The XeF2 molecules has a linear arrangement of atoms.
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