GOALS FOR

Chapter 1 Structure and Bonding

▪ Atomic structure
▪ Bonding
▪ Lewis structure
▪ Resonance
▪ Hybridization
▪ Polar covalent bond

1
 Atomic Structure

12.01
atomic weight

Isotope: 12C(98.9%), 13C(1.1%), 14C(극미량, 반감기: 약 5730년)

Valence electrons are the outer shell electrons of an atom.

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 Periodic Table
Figure 1.1
• Elements in the same row are
similar in size.
• Elements in the same column
have similar electronic and
chemical properties.

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 Electronic configuration rule
1. The Aufbau principle: Lowest energy orbitals are filled first . Thus, 1s orbitals are filled before 2s before 2p before 3s before 3p.
2. The Pauli exclusion principle: A maximum of only two electrons per orbital is allowed and they must have opposite spins.
3. The Hund's rule: Empty orbitals of equal energy take one electron each before pairing occurs.

• Principal quantum number (1,2,3…)

• Angular momentum quantum number (s, p, d, f…)
• Magnetic quantum number (px, py, pz)
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 Bonding

Bonding is the joining of two atoms in a stable arrangement.

Through bonding, atoms gain, lose, or share electrons to attain the electronic
configuration of the noble gas closest to them in the periodic table.
Ionic bonds result from the transfer of electrons from one element to
another.(electrostatic attraction between positively and negatively charged ions)
Covalent bonds result from the sharing of electrons between two nuclei.
Atoms can form either ionic or covalent bonds to attain a complete outer shell
(octet rule for second row elements).

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 Ionic Bonding
When sodium reacts with chlorine the sodium loses one electron to become a cation.

Chlorine gains the electron to become an anion and is then isoelectronic with argon.

Together this forms sodium chloride:

Ionic bonds are common in inorganic chemistry but rare in organic chemistry.
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 Covalent bond

A covalent bond is a chemical bond in which two or more electrons are shared by two atoms.

Octet rule: in forming compounds they gain, lose, or share electrons to give a stable electron configuration
characterized by eight valence electrons. When the octet rule is satisfied for carbon, nitrogen, oxygen, and
fluorine, they have an electron configuration analogous to the noble gas neon.

Single bond Double bond Triple bond

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 Covalent bond
Second row elements can have no more than eight electrons around them. For neutral molecules, this
has two consequences:
• Atoms with one, two, three, or four valence electrons form one, two, three, or four bonds, respectively, in
neutral molecules (e.g., BF3, CH4).

• Atoms with five or more valence electrons form enough bonds to give an octet (e.g., NH3). In this case,
predicted number of bonds = 8 − number of valence electrons.

Unshared electrons are also called lone pairs.

• Figure
1.2

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 Exceptions to the Octet Rule

Elements in Groups 2A and 3A

Elements in the Third Row

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 Lewis structures

Lewis structures are electron dot representations for molecules.

General rules for drawing Lewis structures:

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

• Each single line (-) representing a covalent bond is a shared pair of electrons, called a single bond
• Two lines (=) indicate sharing of four electrons between two atoms, called a double bond; and
three lines(≡) indicate sharing of six electrons between two atoms, called a triple bond.
• Unshared or lone pairs (represented as ':') count two towards the total number of valence
electrons for the nucleus.

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 Lewis Structures
Common Bonding Patterns

Multiple Bonding
Nonbonding Electrons

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 Electronegativity

Electronegativity is a measure of the ability of an element to attract electrons toward itself

when bonded to another element

Figure 1.12

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 Bond Polarity
Electronegativity values are used to indicate whether the electrons in a bond are
equally shared or unequally shared between two atoms.

When electrons are equally shared, the bond is nonpolar.

A C—O bond is a polar covalent bond.

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 Polarity of Molecules

Figure 1.13 Electrostatic potential plot

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출처: [Link] 17
출처: [Link] 18
 Formal Charge

Formal charge is the charge assigned to individual atoms in a Lewis structure.

Formal charge is calculated as follows:

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 Isomers

Sometimes more than one arrangement of atoms (Lewis structure) is

possible for a given molecular formula.

These two compounds are called isomers.

Isomers are different molecules having the
same molecular formula. Ethanol and
dimethyl ether are constitutional isomers.

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 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.

▪ The true structure is a composite of both resonance forms and is called a resonance hybrid.
▪ Resonance allows certain electron pairs to be delocalized over two or more atoms, and this delocalization
adds stability.
▪ A molecule with two or more resonance forms is said to be resonance stabilized.

▪ Resonance structures are not real.

▪ Resonance structures are not in equilibrium with each other.
▪ Resonance structures are not isomers.
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 Drawing Resonance

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 Drawing Resonance

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 Curved Arrow Notation

Curved arrow notation is a convention that shows how electron position differs between two
resonance forms.
Curved arrow notation shows the movement of an electron pair. The tail of the arrow always
begins at the electron pair, either in a bond or lone pair. The head points to where the
electron pair “moves.”

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 Resonance Hybrids

A “better” resonance structure is one that has more

bonds and fewer charges.

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 Molecular Geometry
The most stable arrangement keeps these groups as far away from each other as possible. This is
exemplified by Valence Shell Electron Pair Repulsion (VSEPR) theory.

[Link]

[Link]
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 Molecular Geometry
The most stable arrangement keeps these groups as far away from each other as possible. This is
exemplified by Valence Shell Electron Pair Repulsion (VSEPR) theory.

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 Drawing Three-Dimensional Structures

▪ A solid line is used for a bond in the plane.

▪ A wedge is used for a bond in front of the plane.
▪ A dashed line is used for a bond behind the plane

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 맹독

식용 미나리(출처:[Link] 33
 Orbitals and Bonding: Hydrogen
▪ Covalent bond between two atoms in terms of an in-phase overlap of a half-filled orbital of
one atom with a half-filled orbital of the other

▪ All single bonds are  bonds.

▪ This bond is cylindrically symmetrical because the electrons forming the bond are distributed
symmetrically about an imaginary line connecting the two nuclei.

Electrons feel the attractive force of

the protons

Orbitals begin to overlap

Optimal distance between nuclei

High electron density between the

nuclei
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 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

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 sp3 hybrid orbitals

Linus Pauling proposed a mixing or hybridization of the s and three p

orbitals to create 4 equal unfilled orbitals called sp3 orbitals

• All four sp3 orbitals are of equal energy.

• The axes of the sp3 orbitals point toward the corners of a
tetrahedron.
• σ Bonds involving sp3 hybrid orbitals of carbon are
stronger than those involving unhybridized 2s or 2p
orbitals. 36
Orbital overlap along the internuclear axis (end-on overlap) generates a bond
with rotational symmetry -in this case σ C(2sp3)-H(1s) bond. A tetrahedral
arrangement of four bonds is characteristic of sp3-hybridized carbon.
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 Hybridization and Bonding in Ethane

Rotation occurs around the central C—C  bond.

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sp2 hybrid orbitals

• The 2s and two of the 2p orbitals are mixed to form three sp2 orbitals with a
trigonal planar arrangement.
• The 2pz orbital remains half filled
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Form C-H bonds by
overlap of sp2
and s orbitals

These two half-filled 2p

orbitals have their axes
perpendicular to the
framework of bonds of Each carbon is trigonal planar.
the molecule and
overlap in a side-by- Each carbon is sp2 hybridized.
side (edge-on overlap)
manner to give what is
called a pi (π) bond.

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 No Free Rotation in Ethylene

• Ethane ( bond): Rotation occurs around the central C—C  bond.

• Ethylene (π bond): Unlike the C—C bond in ethane, rotation about the C—C double bond in
ethylene is restricted.
• It can only occur if the π bond first breaks and then reforms, a process that requires
considerable energy.

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sp hybrid orbitals

• The 2s and one of the 2p orbitals are mixed to form two sp orbitals with
a linear arrangement.
• The 2py and 2pz orbitals remain half filled.
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 Summary

참고: [Link]
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 Bond Length and Bond Strength

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 Drawing Organic Molecules: Condensed Structures
• All atoms are drawn in, but the two-electron bond (single bond) lines are generally
omitted.
• Atoms are usually drawn next to the atoms to which they are bonded.
• Parentheses are used around similar groups bonded to the same atom.
• Lone pairs are omitted.

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 Examples of Condensed Structures

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 Skeletal Structures
• Assume there is a carbon atom at the junction of any two lines or at the end of any line.
• Assume there are enough hydrogens around each carbon to make it tetravalent.
• Draw in all heteroatoms and the hydrogens directly bonded to them.

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 Interpreting Skeletal Structures
Figure 1.5

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 Interpreting Skeletal Structures

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