Organic Chemistry

Chapter 1
Introduction and Review
 Definitions
• Old: “derived from living organisms”
• New: “chemistry of carbon compounds”
• From inorganic to organic, Wöhler, 1828
O
+ - heat
NH4 OCN H2N C NH2
urea
=>

Chapter 1 2
 Atomic Structure
• protons, neutrons, and electrons
• isotopes
12 14
6 C 6 C

=>
Chapter 1 3
 Atomic Orbitals

2s orbital (spherical)
=>
2p orbital
Chapter 1 4
 Electronic Configurations
• Aufbau principle:
Place electrons in  
lowest energy
orbital first. 
• Hund’s rule:
Equal energy

orbitals are half-
filled, then filled.
=>
Chapter 1 5
Table 1-1

=>
Chapter 1 6
 Bond Formation
• Ionic bonding: electrons are transferred.
• Covalent bonding: electron pair is shared.

=>

Chapter 1 7
 Lewis Structures
• Bonding electrons
• Nonbonding electrons or lone pairs
H
H
H C O
H

Satisfy the octet rule! =>

Chapter 1 8
Multiple Bonding

=>
Chapter 1 9
 Dipole Moment
• Amount of electrical charge x bond length.
• Charge separation shown by electrostatic
potential map (EPM).
• Red indicates a partially negative region and
blue indicates a partially positive region.

H H
C C
H H
=>
Chapter 1 10
 Electronegativity and
Bond Polarity
Greater EN means greater polarity

=>
Chapter 1 11
Calculating Formal Charge
• For each atom in a valid Lewis
structure:
• Count the number of valence electrons
• Subtract all its nonbonding electrons
• Subtract half of its bonding electrons
3-
H O O
H C C O O P O
H O =>
Chapter 1 12
 Ionic Structures
H H +
-
H C N H Cl
H H

+
_
X
Na O CH3 or Na O CH3

=>
Chapter 1 13
 Resonance
• Only electrons can be moved (usually
lone pairs or pi electrons).
• Nuclei positions and bond angles
remain the same.
• The number of unpaired electrons
remains the same.
• Resonance causes a delocalization of
electrical charge.

Chapter 1
Example=> 14
 Resonance Example
_ _ _
O O O
N N N
O O O O O O

• The real structure is a resonance hybrid.

• All the bond lengths are the same.
• Each oxygen has a -1/3 electrical charge.

=>
Chapter 1 15
 Major Resonance Form
• has as many octets as possible.
• has as many bonds as possible.
• has the negative charge on the most
electronegative atom.
• has as little charge separation as
possible.

Example=>
Chapter 1 16
Major Contributor?

H + H H + H
C N C N
H H H H

major minor,
carbon does
not have octet.

=>
Chapter 1 17
 Chemical Formulas
H O
• Full structural formula H C C O H
(no lone pairs shown)
H
O
• Line-angle formula
OH
• Condensed structural
formula • CH3COOH
• Molecular formula • C2H4O2
• Empirical formula • CH2O
=>
Chapter 1 18
 Calculating Empirical
Formulas
• Given % composition for each element,
assume 100 grams.
• Convert the grams of each element to
moles.
• Divide by the smallest moles to get ratio.
• Molecular formula may be a multiple of
the empirical formula.
=>
Chapter 1 19
Arrhenius Acids and Bases
• Acids dissociate in water to give H3O+ ions.
• Bases dissociate in water to give OH- ions.
• Kw = [H3O+ ][OH- ] = 1.0 x 10-14 at 24°C
• pH = -log [H3O+ ]
• Strong acids and bases are 100%
dissociated.
+ -
HCl + H2O H3O + Cl
1M 1M
=>
Chapter 1 20
 BrØnsted-Lowry
Acids and Bases
• Acids can donate a proton.
• Bases can accept a proton.
• Conjugate acid-base pairs.
O O
- +
CH3 C OH + CH3 NH2 CH3 C O + CH3 NH3
acid base conjugate conjugate
base acid

=>
Chapter 1 21
 Acid and Base Strength
• Acid dissociation constant, Ka
• Base dissociation constant, Kb
• For conjugate pairs, (Ka)(Kb) = Kw
• Spontaneous acid-base reactions
proceed from stronger to weaker.
O O
- +
CH3 C OH + CH3 NH2 CH3 C O + CH3 NH3

pKa 4.74 pKb 3.36 pKb 9.26 pKa 10.64

=>
Chapter 1 22
Determining Relative Acidity

• Electronegativity
• Size
• Resonance stabilization of conjugate
base

=>

Chapter 1 23
 Electronegativity
As the bond to H becomes more
polarized, H becomes more positive and
the bond is easier to break.

=>
Chapter 1 24
 Size
• As size increases, the H is more loosely
held and the bond is easier to break.
• A larger size also stabilizes the anion.

=>
Chapter 1 25
 Resonance
• Delocalization of the negative charge on the
conjugate base will stabilize the anion, so the
substance is a stronger acid.
• More resonance structures usually mean
greater stabilization.

O O
CH3CH2OH < CH3C OH < CH3 S OH
O
=>
Chapter 1 26
 Lewis Acids and Bases
• Acids accept electron pairs = electrophile
• Bases donate electron pairs = nucleophile
_ +
CH2 CH2 + BF3 BF3 CH2 CH2
nucleophile electrophile

=>
Chapter 1 27
End of Chapter 1

Chapter 1 28