CDB 1013 – ORGANIC CHEMISTRY

LECTURE 1.2:
STILL THE BASICS

PROF. DR. MASAHARU KOMIYAMA

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LEARNING OUTCOME
By end of this lecture, student should be
able to

1. Deconstruct hybrid orbitals of simple

organic compounds.
2. Compare and contrast the bond length
and bond strength of common organic
compounds.

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HYBRIDIZATION
At this point, student should be familiar with the
atomic orbitals and electron configurations.

Period 4

Period 3

Period 2

Period 1

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HYBRIDIZATION
At this point, student should be familiar with the
atomic orbitals and electron configurations.

Electron makes pairs.

Covalent bonds are also made with paired electrons
(thus the name “lone” pair for non-bonding pair).

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HYBRIDIZATION
s orbital

p orbitals
(px, py, pz)

d orbitals

f orbitals

Visualizing Electron Orbitals

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HYBRIDIZATION – HYDROGENS
 What orbitals do the first- and second-row atoms use to form bonds?
 Let’s begin with hydrogen and then examine the orbitals used for
bonding by atoms in the second row.

Orbital overlap

 A σ bond concentrates electron density on the axis that joins two

nuclei. All single bonds are σ bonds. Electron cloud of σ bond is
rotationally symmetric with respect to the bond axis.
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HYBRIDIZATION – CH4

px py pz

Why 2px12py1 , not 2px2?

→ Hund's Rule
 This lowest energy arrangement of electrons
for an atom is called its ground state.
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HYBRIDIZATION – CH4

 In this description, carbon should form only two bonds because it

has only two unpaired valence electrons, and CH2 should be a stable
molecule.
 In reality, however, CH2 is a highly reactive species that cannot be
isolated under typical laboratory conditions. In CH2, carbon would
not have an octet of electrons.
In actuality, CH4 is stable, with tetrahedral molecular
structure. Methane also conforms to octet rule.

Then, how?
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HYBRIDIZATION – CH4
 There is a second possibility.
 Promotion of an electron from a 2s to a vacant 2p orbital would
form four unpaired electrons for bonding. This process requires
energy because it moves an electron to a higher energy orbital.
 This higher energy electron configuration is called an
electronically excited state.

 This description is still not adequate. Carbon would form two different
types of bonds: three with 2p orbitals and one with a 2s orbital. But
experimental evidence points to carbon forming four identical bonds
in methane.
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HYBRIDIZATION – CH4
 To solve this dilemma, Prof. Linus Pauling, two times Nobel Laureate,
has proposed that atoms like carbon do not use pure s and pure p
orbitals in forming bonds. Instead, atoms use a set of new orbitals
called hybrid orbitals.
 The mathematical process by which these orbitals are formed is called
hybridization.

Note that sp3 energy level is lower than that of 2p,

compensating the energy used to create exited state.
 These hybrid orbitals are called sp3 hybrids because they are formed
from one s orbital and three p orbitals.

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HYBRIDIZATION – CH4
 What do these new hybrid orbitals look like?

109.47

 The four hybrid orbitals form four equivalent bonds.

We can now explain the observed bonding in CH4.
 Each bond in CH4 is formed by overlap of an sp3 hybrid
orbital of carbon with a 1s orbital of hydrogen.
 These four bonds point to the corners of a
tetrahedron.

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HYBRIDIZATION – sp2 and sp

 One 2s orbital and three 2p orbitals form four sp3 hybrid orbitals.
 One 2s orbital and two 2p orbitals form three sp2 hybrid orbitals.
 One 2s orbital and one 2p orbital form two sp hybrid orbitals.
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How double bond is formed?

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How triple bond is formed?

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CLASS ACTIVITY 1.5
Draw the hybrid orbitals for the following compounds

1. NH3
2. H2O

3. BF3

4. H2C=CH2

5. HC≡CH

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CLASS ACTIVITY 1.5 - ANSWER

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CLASS ACTIVITY 1.5 - ANSWER

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HYBRIDIZATION – SUMMARY

 The σ bond is formed from the end-on overlap of Csp2 – Osp2.

 The π bond is formed from the side-by-side overlap of C2p – O2p.
 The O atom has three sp2 hybrid orbitals.
 One is used for the σ bond of the double bond.
 The remaining two sp2 hybrids are occupied by the lone pairs.
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BOND LENGTH AND BOND STRENGTH

You should NOT remember the values,

but MUST understand it…
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BOND LENGTH AND BOND STRENGTH
 Bond length is the average distance between the centers of two
bonded nuclei.

 As the number of electrons between two nuclei increases, bonds

become shorter and stronger.
 Thus, triple bonds are shorter and stronger than double bonds,
which are shorter and stronger than single bonds.

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BOND LENGTH AND BOND STRENGTH
 A Comparison of Carbon–Hydrogen Bonds
The length and strength of a C – H bond vary slightly depending
on the hybridization of the carbon atom.

Uhm… why?
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BOND LENGTH AND BOND STRENGTH
 To understand why this is so, we must look at the atomic orbitals used
to form each type of hybrid orbital.
 A single 2s orbital is always used, but the number of 2p orbitals varies
with the type of hybridization. A quantity called percent s-character
indicates the fraction of a hybrid orbital due to the 2s orbital used to
form it.

Simple positional problem.

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BOND LENGTH AND BOND STRENGTH

 Learn the general trends. Often knowing such trends is more

useful than learning a set of exact numbers, because we are
usually interested in comparisons rather than absolute values.

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BOND LENGTH AND BOND STRENGTH
 Bond length decreases across a row of the periodic table as the size of
the atom decreases.

 Bond length increases down a column of the periodic table as the size of
an atom increases.

The larger the atom size, the larger the volume

of electron cloud, and thus longer bond length,
weaker bond strength.
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BOND ANGLE
 Bond angle determines the shape around any atom bonded to two
other atoms. To determine the bond angle and shape around a given
atom, we must first determine how many groups surround the atom.
 A group is either an atom or a lone pair of electrons. Then we use the
valence shell electron pair repulsion (VSEPR) theory to determine the
shape.
 VSEPR is based on the fact that electron pairs repel each other; thus:
the most stable arrangement keeps these groups as far away from
each other as possible.

2: linear, 3: plane triangle, 4: tetrahedron

5: tetragonal bipyramid, 6: octahedron, 7: pentagonal bipiramid 25
BOND ANGLE (CONT.)

117.4

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BOND ANGLE (CONT.)

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BOND ANGLE (CONT.)

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CLASS ACTIVITY 1.6
Determine the geometry around all second-row elements in each compound.

1. NH2

2. H2O

3. CO2

4. NH4+

5. Predict the geometry around each indicated atom.

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CLASS ACTIVITY 1.7
The principles learned in this chapter apply to all organic molecules regardless of size
or complexity.

You should be able to do all of the following:

 Convert this skeletal structure of the following compounds to a Lewis structure.
 Determine the hybridization and geometry around every atom.
 Compare bond length and bond strength for certain bonds.

L-dopa
drug used to treat Parkinson’s disease)

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SELF ASSESSMENT

Self Assessment

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SELF ASSESSMENT
SCORE
Learning Outcome
1 2 3 4 5
To write electron configuration for any given atom
To draw chemical structures of organic compounds
and its derivatives using several methods.
Lecture 1.1

To calculate formal charges of each atom in the

chemical compounds, particularly organic
compounds.
To discuss the difference methods to draw chemical
structures.
To explain stability of organic compounds through
their resonance structures.
To deconstruct hybrid orbitals of simple organic
Lecture 1.2

compounds.
To compare and contrast the bond length and bond
strength of common organic compounds.

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