Chapter 1

Introduction and Review

Chapter 1 1
 Organic Chemistry
O

H H CH3 O
S O C6 H5 O O OH
CH3CH2CH CHCH2CONH
CH3
N H5 C6 N O
O COONa
H OH
HO
O
2-Pentenylpenicillin H5C6 O O
CH3O
O
O CH3
O H
NCH3 Taxol
HO
Codeine

• Organic chemistry is the chemistry of carbon

compounds.
Chapter 1 2
 Isotopes

12 14
6 C 6 C

• Isotopes are atoms with the same number of

protons but different number of neutrons.
• Mass number is the sum of the protons and
neutrons in an atom.

Chapter 1 3
Electronic Configurations of Atoms
• Valence electrons are electrons on the
outermost shell of the atom.

Chapter 1 4
 Ionic Bonding
• To obtain a noble gas
configuration (a full valence
shell), atoms may transfer
electrons from one atom to
another.
• The atoms, now bearing
opposite charges, stay
together by electrostatic
attraction.

Chapter 1 5
 Covalent Bonding
• Electrons are shared between the atoms to complete
the octet.
• When the electrons are shared evenly the bond is said
to be nonpolar or pure covalent.
• When electrons are not shared evenly between the
atoms, the resulting bond will be polar (refer to
electronegativity table)

Chapter 1 6
• How to draw Lewis Structures of Covalent compounds:
• 1. Place the least electronegative element (or the
element by itself) in the center (never hydrogen).
• 2. Add the # of valence electrons. Adjust for any charge.
• 3. Draw single covalent bonds between the central atom
and surrounding atoms.
• 4. Complete the octet of the surrounding atoms using
lone pairs.
• 5. Place any extra electrons on the central atom.
• 6. Complete the octet of the central atom by forming
double or triple bonds using lone pairs of the surrounding
atoms.

Chapter 1 7
 Lewis Structures
CH4 NH3
H
H N H
H C H H
H

H2O Cl2
H O H Cl Cl
Chapter 1 8
Double and Triple Bonds

Chapter 1 9
 Bonding Patterns
Valence # Bonds # Lone Pair
electrons Electrons

C 4 4 0

N
5 3 1

O
6 2 2
Halides
(F, Cl, Br, I) 7 1 3

Chapter 1 10
Lone Pairs

Chapter 1 11
 Electronegativity and Bond
Polarity
• Electronegativities can be used to predict whether
a bond will be polar.
• Since the electronegativity of carbon and
hydrogen are similar, C—H bonds are considered
to be nonpolar.

Chapter 1 12
 Dipole Moment
Bond polarity is measured by dipole moment. It is
expressed in debyes (D), where 1D = 3.336 x 10 -30
coulomb meter (C.m)

• Dipole moment = amount of charge separation x

bond length.
Chapter 1 13
 Charged Species
Formal charge = number of valence electrons – ( e in lone pairs + # bonds)

H3O+ NO+
6 – (2 + 3) = +1 6 – (2 + 3) = +1

+
H O H N O
+
5 – (2 + 3) = 0
H

O
HCO 3
-
C
6 – (6 + 1) = -1
O OH
Chapter 1 14
 Solved Problem 1
Compute the formal charge (FC) on each atom in H 3N – BH3.

Solution

Chapter 1 15
Common Bonding Patterns

Chapter 1 16
 Resonance Forms
• In a resonance form, only the electrons are
moved. Connectivity between atoms stay the
same.
• The real structure is a hybrid of the different
resonance forms.
• Arrows connecting resonance forms are double
headed.
• Spreading the charge over two or more atoms
stabilizes the ion.

Chapter 1 17
 Resonance Forms
Major resonance form will have:
– 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.

Chapter 1 18
 Major and Minor Contributors
• The major contributor is the one in which
all the atoms have a complete octet of
electrons.
O O
C C
H H H H
MAJOR MINOR

The carbon atom does

not have a complete
octet of electrons.

Chapter 1 19
 Major and Minor Contributors
(Continued)
• When both resonance forms obey the octet rule, the major contributor is
the one with the negative charge on the most electronegative atom.
Consider cyanate ion:
•

N C O N C O
MAJOR MINOR

The oxygen is more electronegative,

so it should have the negative
charge.
Chapter 1 20
• Consider this organic nitrite:

CH3 O N O CH3 O N O
MAJOR MINOR

The most stable one is the one with the smallest

separation of oppositely charged atoms.

Chapter 1 21
 Solved Problem 2
Draw the important resonance forms for [CH3OCH2]+. Indicate which structure is major and minor 
contributor or whether they would have the same energy.

Solution

The first (minor) structure has a carbon atom with only six electrons around it. The second (major) 
structure has octets on all atoms and an additional bond.

Chapter 1 22
 Solved Problem 3
Draw the resonance structure the compound below.  Indicate which structure is major and minor 
contributor or whether they would have the same energy.

Solution

Both of these structures have octets on oxygen and both carbon atoms, and they have the same number 
of bonds. The first structure has the negative charge on carbon; the second has it on oxygen. Oxygen is 
the more electronegative element, so the second structure is the major contributor.

Chapter 1 23
 Resonance Forms

• The true structure will be a hybrid between the

contributing resonance forms.

Chapter 1 24
 Resonance Forms for the
Acetate Ion

• When acetic acid loses a proton, the resulting acetate

ion has a negative charge delocalized over both of the
oxygen atoms.
• Each oxygen atom bears half of the negative charge,
and this delocalization stabilizes the ion.
• Each of the carbon–oxygen bonds is halfway between a
single bond and a double bond.
Chapter 1 25
 Structures and Formulas
Lewis Structure Condensed

H H
1 2
H C C H CH3CH3
H H

H H H H
1 2 3 4
H C C C C H CH3CH2CH2CH3
H H H H
Chapter 1 26
 Structures and Formulas
Lewis Structure Condensed

H H Br H Br
1 2 3 4
H C C C C H CH3CH2CHCH3
H H H H

H H O H O
1 2 3 4
H C C C C H HOCH2CH2CCH3
OH H H
Chapter 1 27
 Line-Angle Formula or Skeletal
Structure or Stick Figure
H H H H
1
H C C C
2 3
C H
4 C C
C C
H H H H

H H H H H O 1 2 3 4 5 6
1 2 3 4 5 6 O
H C C C C C C
H H H H H H H

Chapter 1 28
Examples of Condensed Structural
Formulas

Chapter 1 29
Examples of Condensed Structural Formulas

Chapter 1 30
Examples of Line Angle Formulas

Chapter 1 31
Calculating Empirical Formulas
The following are items that need to be
considered when 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 32
 Arrhenius Acids
• Arrhenius acids are substances that
dissociate in water to give H3O+ ions.

Chapter 1 33
 Arrhenius Bases
• Arrhenius bases are substances that
dissociate in water to give hydroxide ions.

Chapter 1 34
Brønsted-Lowry Acids and Bases
Brønsted-Lowry acids are any species that donate a proton.
Brønsted-Lowry bases are any species that can accept a proton.

Chapter 1 35
 Conjugate Acids and Bases

• Conjugate acid: when a base accepts a proton, it

becomes an acid capable of returning that proton.
• Conjugate base: when an acid donates its proton, it
becomes capable of accepting that proton back.

Chapter 1 36
 pKa
• 1. Lower the pKa, stronger the acid.
• 2. Higher the Ka, stronger the acid.
• 3. Stronger the acid, weaker will be its
conjugate base (Ka.Kb = 1x 10-14)
• 4. In an acid-base reaction, the reaction
proceeds from strong acid and base to
weak acid and base.

Chapter 1 37
 -
CH3COO + CH3OH CH3COOH + CH3O-
pKa of pKa of
CH3OH is 15.5 CH3COOH is 4.74

Since acetic acid is a stonger acid acetate ion will be a weak base in this reaction
Methanol is a weaker acid so methoxide ion will be a stronger base
The equilibrium will favor reactants

Chapter 1 38
 Structural Effects on Acidity
1. Effect of Electronegativity on pKa
Across a period
• As the bond to H becomes more polarized, H becomes
more positive and the bond is easier to break.

Chapter 1 39
 2. Effect of Size on pKa
Down a Group

• As size increases, the H is more loosely held and the bond is

easier to break.
• A larger size also stabilizes the anion.
• Conclusion: Acidity increases as you go from left to right within a period
(electronegativity). Acidity also increases as you go down a group (size).

40
Chapter 1
 3. Effect of Resonance on pKa

• If the negative charge on an atom can be delocalized over two or

more atoms, the acidity of that compound will be greater than when
the negative charge cannot be delocalized.
• The ethoxide anion is less acidic than the acetate ion simply
because the acetate ion can delocalize the negative charge.
• Methanesulfonic acid can delocalize the charge in three different
resonance forms, making it more acidic than the acetate ion.
Chapter 1 41
 Nucleophiles and Electrophiles
• Nucleophile: Donates electrons. Also known as
Lewis bases.
• Electrophile: Accepts electrons. Also known as
Lewis acids.
• When forming a bond, the nucleophile attacks
the electrophile, so the arrow goes from negative
to positive.
• When breaking a bond, the more electronegative
atom receives the electrons.

Chapter 1 42
Curved -arrow formalism to show movement of
electron pairs

Chapter 1 43