Chapter 2: Organic Compounds: A First Look

Common Bonding Situations

Hydrogen 1 bond H O H

Carbon 4 bonds (neutral and 8 electrons)

H H
H H
H C C H C C H C C H
H H H H
4 single bonds double bond triple bond

Reactive Carbon Species

H H H
_
H C+ H C H C
H H H
carbocation radical carbanion
Nitrogen 3 bonds and one unshared pair of electrons

H H
H C N H C N H C N
H H H H

Other relatively stable species

H _
+ H N
H N H
H H
4 bonds 2 bonds
+ charge 2 pairs
- charge
Oxygen 2 bonds and 2 unshared electron pairs

H H
H C O H C O
H H

Other relatively stable species

+ _
H O H H O
H
3 bonds 1 bond
1 pair 3 pairs
+charge
- charge
hydronium ion
Halogens 1 bond and 3 unshared electron pairs

H
H C Br
H

also 4 unshared pairs and negative charge

_
Cl
Phosphorus
three bonds and an unshared pair of electrons (like N)
also can have more than 8 electrons in its valence shell

Sulfur two bonds and two unshared electron pairs (like O)

also can have more than 8 electrons in its valence shell

Bond Strengths and Bond Lengths
Bond Dissociation Energy: energy that must be added to break
a bond in a homolytic fashion
(one electron with each atom)
1. Stronger bonds are shorter.

2. C-H, N-H, O-H: 90-110 kcal/mol;

o
1 A(10-10 m, 100 pm)

3. C-C, C-N, C-O: 65-80 kcal/mol;

o
1.5 A
4. Bonds become weaker and
longer down a column

5. C=C is stronger and shorter

than C-C (but not two times)
C=O is very strong and very
common
Constitutional Isomers

C 2H 6O

H H H H
H C C O
O H H C O C H
H H H H
ethanol dimethyl ether
ethyl alcohol gas
liquid poisonous

Constitutional Isomers (Structural Isomers):

compounds with the same molecular formula but different
arrangements of bonded atoms
(different structures, different connectivities)
Constitutional isomers have different properties
and different chemical reactions.
Hydrocarbons: compounds containing only C and H

Formula Number of Constitutional Isomers

CH4 1
C2 H6 1
C3 H8 1
C4H10 2
C5H12 3
C6H14 5
C7H16 9
C10H22 75
C20H42 366,319
C30H62 4,111,846,763
 C6H14 (5 isomers) H H
H C C H
H H H H H H H H H H
H C C C C C C H H C C C C H
H H H H H H H H H H
straight chain same
H
H H
H C H
H C H
H C H
H H H H H H H H H H H H
C C
H C C CC CC CC H H C
C C C C
C CC H H CC C
C C C C H
H H H H H H H H H H H H H H H
branched

same
 C
C C
C

C C
C CC CC C C
C C C CC C C
C CC CC

C C
C5H12 3 isomers C5H11Cl 8 isomers
C6H14 5 isomers C6H12 many

H H H H
H C C C C C C H
-2 H H H H H H H
H H H H H H
H C C C C C C H C6H12
H H H H H H H H
-2 H H H
C6H14 C
H C C H
H C C H
C H
H
H H
C6H12
C6H14 is saturated (has the maximum number of H’s for six C’s).

C C C C C C

General formula = CnH2n + 2

for a hydrocarbon
with maximum H’s
(saturated)

Remove two H’s to introduce one C=C or one ring.

The resulting structure is unsaturated.
Degree of Unsaturation (DU)

DU = total number of rings plus double bonds

(maximum H's) - (actual H's)

DU =
2

(2n + 2) - (x)
for CnHx DU =
2
 C7H14 DU = (2)(7) + 2 - 14 = 1
2
So there is one ring or one double bond in C7H14.

H H H H H H H
line structure
H C C C C C C C H or Kekule structure
H H H H H

H2C CHCH2CH2CH2CH2CH3
or condensed
structure
CH2 CHCH2CH2CH2CH2CH3
or
CH2 CH(CH2)4CH3

skeletal
structure
 H
H
H H C H H H CH3
H C C C C C C H CH3CH2C CHCH2CH3
H H H H H
DU with Other Elements Present

halogen monovalent, replaces H one for one,

so count as H Br
DU = 2(6) + 2 –10 =2
C6H9Br = C6H10
2

oxygen divalent, can insert between two atoms without

changing number of H’s, so ignore
O
C 5H8 O = C5H8 DU = 2(5) + 2 – 8 = 2
2
nitrogen trivalent, if N is added, must add one more H,
so increase maximum H’s by one for each N

C8H13N DU = (2)(8) + 2 + 1 – 13
=3
2

or subtract NH from the formula

C8H13N = C8H12 DU = (2)(8) + 2 – 12

=3
2

N
C (triple bond counts as two DUs)
Physical Properties and Molecular Structure
melting point, boiling point, solubility

Intermolecular Forces
charge interactions larger charges = stronger interaction

Type Example

very strong
ion-ion ionic bond
188 kcal/mol

moderately strong
ion-dipole
dipole-dipole weak

dipole-induced dipole weaker

instantaneous dipole-
induced dipole weakest
(London Force)

Together these last three are called

van der Waals forces (0.5 – 5 kcal/mol).
Hydrogen Bonding

Hydrogen bonds are stronger than other dipole-dipole

attractions because the small size of H allows less distance
between the charges (3 – 8 Kcal/mol).
Melting Points
increase with stronger intermolecular forces
increase with more symmetrical shape
(molecules pack better into crystal lattice)

compound melting point

NaCl 801oC ionic compound

CH3CH2CH3 -190oC nonpolar

CH3(CH2)3CH3 -130oC larger, more London forces

CH3
H3C C CH3 -71oC more symmetrical

CH3
O
CH3CH2CH2CH -99oC has polar bond
Boiling Points
increase with stronger intermolecular forces
increase with more surface area (more London forces)
(rod shaped)
increase with hydrogen bonding

compound boiling point

NaCl 1413oC ionic compound

CH3CH2CH3 -42oC nonpolar

CH3(CH2)3CH3 36oC larger, more London forces

CH3(CH2)3CH3 36oC larger, more London forces

CH3
H3C C CH3 10oC less surface area
CH3
O
76oC more polar
CH3CH2CH2CH

OH
CH3CH2CH2CH2 117oC hydrogen bonding
Solubility
Like dissolves like.
Polar compounds dissolve in polar solvents.
Nonpolar compounds dissolve in nonpolar solvents.

NaCl dissolves in water.

NaCl does not dissolve in CH3(CH2)3CH3.

CH3(CH2)3CH3 and water do not mix (form two layers).
CH3CH2OH mixes with water in all proportions.

CH3CH2CH2CH2OH is slightly soluble in water (7.4 g/100 mL).

Functional Groups
Chemical reactions usually occur at or near polar bonds.

CH3CH2CH2OH CH3CH2CH2CH2OH

alkyl group: C’s singly bonded to other C’s and H’s

(carbon skeleton or carbon framework)
general representation: R-

functional group: where chemical reactions occur

(double bonds, triple bonds, polar bonds, etc.)

R-OH alcohol functional group

O
R COH carboxylic acid functional group