10

Consider the following anion CH3CH = CHCH2:

Use the arrow pushing technique to write another resonance structure.

O O

Consider the following anion C C

CH3 C CH3
H

Use the arrow pushing technique to write two other resonance structures.

.
Consider the pentadienyl radical, CH2 = CHCH = CHCH2
 11

CONSTITUTIONAL (STRUCTURAL) ISOMERS

•   These are molecules that differ in their structure or connectivity.
•   They have the same molecular formula.
•   They have different physical properties, such as m.p. and b.p., and different
chemical reactivities.
Example: The molecular formula of C3H7Cl has two constitutional isomers.
Write the Lewis structures (extended structural formulas).
1-chloropropane, b.p. 46oC 2-chloropropane, b.p.36oC

Example: Draw Lewis structures for the three isomers having the molecular
formula C3H8O.
 12

Example: The molecular formula of C4H10 has two constitutional isomers.

N.B. The molecules of the branched chain isomer are more spherical in shape than
straight chain molecules so they will not tangle as much with their sister
molecules. As a result, dispersion forces are weaker and a lower boiling point
results.
 13

CONDENSED STRUCTURAL FORMULA

•   This is a condensed way of writing a Lewis structure.
Consider 2-chloropropane and isobutane.

Molecular Formula Lewis structure Condensed Structural Formula

C2H6O

C3H6Br2
 14

BOND-LINE STRUCTURES / SKELETAL STRUCTURES

•   Show only the carbon skeleton.

•   C and H are usually not shown but other atoms are shown.
Examples: Skeletal structure
Propane CH3CH2CH3

2-Bromopropane CH3CH(Br)CH3

Dimethylamine (CH3)2NH

Triethylamine (CH3CH2)3N

Ethanol CH3CH2OH

Methylclobutane CH2 CHCH3

CH2 CH2

3-Bromo-1-pentene CH2 = CHCH(Br)CH2CH3

CH3CHCH2CH(OH)CH = C(CH3)2

CH2N(CH3)2

(CH 3)2C C(C2H 5)

CH(CH 3)2

CH3CH2C CCH2CH2CH 3
 15

COMMON FUNCTIONAL GROUPS

•   A functional group is a group of atoms that behaves in a certain way chemically.
•   The functional group determines the chemistry of a molecule.
FUNCTIONAL GROUPS FAMILY NAME

C C                                carbon-­carbon  double  bond                                            Alkene

C C triple  bond                                                                              Alkyne

C OH hydroxyl  group                                                                                Alcohol

C C H                                                                                                          Aldehyde
to  at  least  one  H  atom
carbonyl  group  is  bonded  to  at  least  one  hydrogen  atom.

O
   Ketone
C C C
carbonyl  group  is  bonded  to  two  carbon  atoms.

C O C Ether

C C O H carboxyl  group                                                            Carboxylic  Acid

R C O R' Ester

R C NH2 Amide

C N nitrogen  is  bonded  to  at  least   Amine

one  carbon  atom

The  aromatic  ring  is  the   Arene

functional  group.  
Note:  C6H6  is  benzene.
 16

ORGANIC COMPOUNDS AS ACIDS AND BASES

Bronsted-Lowry concept (1923 A.D.)
•   An acid is a proton donor
•   A base is a proton acceptor.
Lewis acids, bases; the arrow pushing (curved arrows) technique.
•   A base is an electron pair donor.
•   An acid is an electron pair acceptor.
N.B. We will see below that water can act as an acid or base. It is said to be
amphiprotic.
Conjugate acid-base pairs are species that differ only by H in their formula.
1. H2O(l) + HCl(g) H3O+(aq) + Cl-(aq)

2. NH3(g) + H2O(l) NH4+(aq) + OH-(aq)

3. CH3CO2H + H2O CH3CO2- + H3O+

 17

ACID STRENGTH
•   HCl is a strong acid because it ionizes completely in water.
HCl + H2O H3O+ + Cl-

Ka = [H3O+] [Cl-] / [HCl] = 1 X 107

•   Ka is called the acidity constant or the acid dissociation constant. Thus a
large Ka value means that a great deal of ionization has occurred and much
H3O+ has been produced. This means that the acid is a strong acid.

•   The term pKa can also be used to denote the strength of an acid.
pKa = - log Ka

Thus for HCl, pKa = -log (1 X 107) = -7 and HCl is a strong acid.
Acetic acid, CH3CO2H; Ka = 1.8 X 10-5 ; pKa = 4.74. Acetic acid is a weak acid.
Problem: Which is the stronger acid: formic acid, HCO2H (pKa = 3.7) or picric
acid, C6H3N3O7 (pKa = 0.3)? Write equations for their ionization.

Problem: The pKa of water is 15.74 and that of ethanol is 16.00. Which is the
stronger acid? Write a possible reaction that could occur when the two substances
are mixed?

Problem: On which side (products or reactants) does the following equilibrium

rest?
CH3CO2H + OH- CH3CO2- + H2O
pKa = 4.74 pKa = 15.7
Factors affecting acidity (4)
 18

1. The electronegativity of the atom bonded to H.

Increasing acid strength

CH4 < NH3 < H2O < HF

Non acids hydrofluoric acid
Consider the stability of the conjugate base in each case.
HF H+ + F-

H2O H+ + OH-

The conjugate base F- is more stable than the conjugate base OH- because F is
more electronegative than O and is thus better able to accommodate a negative
charge.

Likewise, since N is more electronegative than C, the conjugate base NH2- is more
stable than the conjugate base CH3-. So NH3 is more acidic than CH4. In fact, CH4
and other alkanes, as well as NH3, are not called acids.

2. Increasing acid strength

HI > HBr > HCl > HF

HI H+ + I- vs. HF H+ + F-

Rationale: here the large size of the I- can easily disperse the negative charge over
its large surface. However the small size of the F atom means that the negative
charge on F- is localized or concentrated in a smaller region of space. This makes I-
a weaker base than F-, so HI is a stronger acid than HF.

3. Inductive effects; resonance effects

Note the acidity of the following compounds.
Increasing acidity

CH3CH2OH < CH3CH(F)OH < CH3CO2H < FCH2CO2H

Consider the stabilization of the ethoxide ion due to the electron withdrawing
inductive effect of the F atom.
 19

Also consider resonance stabilization of the fluoroacetate ion, FCH2CO2-.

H
H O
O
F C C
F C C
O
O
H H

4. Hybridization of carbon has an effect on acidity.

Ka pKa
-60
CH4 1 x 10 60

H2C = CH2 1 x 10-44 44

H C C H 1 x 10-25 25

The above data shows that the three hydrocarbons are essentially non acidic.
However, of the three, acetylene, C2H2, is the strongest acid.
Consider what happens if CH4 acts as an acid and loses a proton. The resulting
methyl anion is a very strong base as the lone pair is in an sp3 orbital that extends
far from the nucleus and thus can easily be donated to a positive species such as
H+. As a result CH4 is not acidic.
Sketch:

Compare with the anion that results when acetylene loses a proton, The resulting
acetylide anion has a lone pair of electrons in a sp hybrid orbital which is relatively
close to the carbon nucleus. So the lone pair is less easily donated, the anion is less
basic and as a result C2H2 is more acidic than CH4.
Sketch:
 20

BASE STRENGTH (IMPORTANT)

•   The usual strong bases are NaOH and KOH. They are often in aqueous
solution where the basic species is the hydroxide ion, OH-.
•   Other stronger bases are:
1. Sodium alkoxides such as
a) sodium methoxide, written as NaOCH3, or CH3ONa
where the basic species is the methoxide anion, CH3O-.
b) sodium ethoxide, NaOCH2CH3, or CH3CH2ONa, or C2H5ONa.
where the basic species is the ethoxide ion, CH3CH2O-.

2. Sodium amide, NaNH2, where the basic species is the amide ion, NH2-.
NH2- is a stronger base than CH3O-. (N is less electronegative than O).
Example: NaNH2 + HCO2H

3. Alkyllithium and alkylsodium compounds.

a) methylsodium, CH3Na, where CH3- , the methyl anion, is a very strong base.

b) ethyllithium, CH3CH2Li, where CH3CH2-, the ethyl anion, is a very strong base.

4. Sodium hydride, NaH i.e. Na+H- The hydride ion is a very strong base.

Problems: Write the products expected in each of the following reactions; then
write the net ionic equation using the arrow pushing technique.
NaNH2 + CH3OH
 21

CH3Na + CH3CO2H

NaH + H2O

Add all missing lone pairs in the following reaction. Identify the Lewis acid and
Lewis base. Write the arrow pushing mechanism.
H F H F

H N B F H N B F
+
H F H F

CH3CH2OH + H2SO4 CH3CH2OH2+ + HSO4-

ethanol ethyl oxonium ion
(protonated ethanol)
Add all missing lone pairs to each reactant and product.
Identify the Bronsted acid and Bronsted base. Write the arrow pushing mechanism.
O

An acceptable structure for H O S O H

sulfuric acid is shown.
O
22