[Lecture Note]

유기 화학 I (CHE2102)
Chapter 1 : Structure and Bonding

1.1 The Periodic Table

- Atom : nucleus (protons+neutrons) + electron
- Atomic number: number of protons
Mass number: number of protons plus neutrons
- Cation (+): fewer electrons than protons
Anion (-): more electrons than protons
- Isotopes: same element having a different number of neutrons (different mass number)
- Periodic Table
Row: similar in size / column: similar electronic and chemical properties

- Atomic orbitals

- 1st row: H, He, one orbital(1s), maximum two electrons

- 2nd row: one 2s orbital, and three 2p orbitals, 8 valence electrons
1.2 Bonding
- Bonding: joining of two atoms in a stable arrangement, gain, lose, or share electrons
- Octet rule: form either ionic or covalent bonds to attain a complete outer shell (8 electrons for
2nd row elements)
- Ionic bonds: transfer of electrons from one element to another, cation and anion formed
Covalent bonds: sharing of electrons between two nuclei
(between elements having similar electronegativity)
- Bond number
Atoms with one, two, three, or four valence electrons: form one, two, three, or four bonds,
respectively (ex: BF3, CH4)
Atoms with five or more valence electrons: number of bonds = 8 – number of valence electrons
- Lone paris: nonbonded electrons

1.3 Lewis Structure

- Lewis structure
1. Draw only the valence electrons.
2. Give every second-row element no more than eight electrons.
 3. Give each hydrogen two electrons.

- Multiple bonds: If all valence electrons are used and an atom does not have an octet, form multiple
bonds (see Sample Problem 1.2)
- Formal charge: the charge assigned to individual atoms in a Lewis structure

(“owns”: unshared electrons + half of its shared electrons)

1.4 Isomers
- Isomers: different molecules (arrangement of atoms in Lewis structure) having the same molecular
formula (ex: ethanol vs. dimethyl ether)

1.5 Exceptions to the Octet Rule

- Elements in Groups 2A and 3A (lower valence electrons)
- Elements in the Third Row (because of d orbital)

1.6 Resonance
- Resonance structures (also, resonance forms): same placement of atoms but a different
arrangement of electrons

- Resonance hybrid: not individually separated two form, electron pairs to be delocalized over two
or more atoms, and this delocalization adds stability
- Resonance structures are not isomers!
- How to draw resonance structure
Rule [1]: Two resonance structures differ in the position of multiple bonds and nonbonded
electrons. The placement of atoms and single bonds always stays the same.

Rule [2]: Two resonance structures must have the same number of unpaired electrons.

Rule [3]: Resonance structures must be valid Lewis structures. Hydrogen must have two electrons
and no second-row element can have more than eight electrons.

- Curved arrow notation: the movement of an electron pair

- Resonance structures can have an atom with fewer than 8 electrons, but can never have a second-
row element with more than 8 electrons (no room for 2p orbitals).

- A “better” resonance structure is one that has more bonds and fewer charges.

1.7 Determining Molecular Shape

- No geometric information in Lewis structure
- Bond length: decreases across a row of the periodic table (higher Z)
increases down a column of the periodic table (more electron shell)
- Valence Shell Electron Pair Repulsion (VSEPR) theory: The most stable arrangement keeps these
groups (atom+lon pair) as far away from each other as possible

- 3D structure: using solid line (bond in the plane), wedge (bond in front of the plane), and dashed
(bond behind the plane)

- In both NH3 and H2O, the bond angle is smaller than the theoretical tetrahedral bond angle
because of repulsion of the lone pairs of electrons.

1.8 Drawing Organic Structures

- Condensed structures (see Figure 1.3 and 1.4)

- Skeletal structure (see How To in p.33)

- Charges and lon pairs in skeletal structure

1.9 Hybridization
- Sigma (σ) bond: concentrates electron density on the axis that joins two nuclei, all single bonds
are σ bond
- Ground state (lowest energy arrangement of electrons) of carbon can make only two σ bonds (it
is not ture!)

- Excited state of carbon can make four σ bonds, but cannot make tetrahedral geometry (real
structure of methane)
- To resolve this dilemma, “hybridization” concept was proposed.
- Bonding in CH4 using sp3 hybrid orbitals

- sp2 and sp hybrid orbitals

- Examples of molecules having hybrid orbitals

1.10 Ethane, Ethylene, and Acetylene

- Ethane (sp3)

Rotation occurs around the central C—C σ bond

- Ethylene (sp2)

No free rotation in ethylene

- Acetylene (sp)
1.11 Bond Length and Bond Strength

- Tendency in hybridization

- S-character (s orbital is more stable than p orbital)

1.12 Electronegativity and Bond Polarity

- Electronegativity: measure of an atom’s attraction for electrons in a bond

- Nonpolar bond, when electrons are almost equally shared (ex: C-C, C-H)
- Polar bond, when atoms of different electronegativity values results in unequal sharing of electrons
- Polarity of molecules: electronegativity difference + direction (cancel or reinforce)