HYDROCARBONS, THE

FIRST FAMILY
Experiment 6
PREPARATION OF ACETYLENE
(ETHYNE)
Hydrocarbons -- contains only C and H atoms
Classifications:
1. Alkanes
- C-C sigma and C-H sigma bonds;
sp3 hybridized
- undergo reactions involving free
radicals
2. Alkenes
- Csp2-Csp2 orbital overlap
- undergo electrophilic addition
3. Alkynes
- 2 pi bonds and 1 sigma bond
- undergoes electrophilic addition

4. Aromatic Hydrocarbons
- presence of pi system of electrons
Types of Reactions:
1.) Alkanes:
Halogenation
- free radical substitution
- Br2/CCl4
-positive test: loss of red-orange
color of molecular bromine and the
evolution of gas
2.) Alkenes:
Addition reactions
- electrophilic addition
a. ) Br2/CCl4 (does not require the presence of
light)
- positive test: loss of the red-orange color of
molecular bromine and the evolution of gas
b.) Baeyer’s reagent (cold, dilute neutral
aqueous KMnO4)
- positive test: loss of purple color and the
formation of a brown precipitate (MnO2)
3.) Alkynes
- electrophilic addition
Halogenation
- 2 Br2/CCl4 (does not require the presence
of light)
- positive test: loss of red-orange
molecular bromine and evolution of gas
Oxidation
- Baeyer’s reagent (cold, dilute, neutral
aqueous KMnO4)
- positive test: loss of purple color;
formation of brown ppt
Ammoniacal AgNO3
- test for terminal alkynes
- release of terminal proton of the alkyne
- positive test: insoluble Ag+ ppt
(acetylide ion)
 Solubility Tests
A. Investigation of Hydrocarbons
1. Physical Properties
Solubility Physical Density
color
in water state in water
Cyclohexane - liquid less colorless
Cyclohexene - liquid less colorless
Benzene - liquid less colorless
2. Halogenation: Reaction with bromine

In the dark Light

Cyclohexane Red-orange Colorless

Cyclohexene Colorless Colorless

Benzene Red-orange Red-orange

Reactions Involved:
Br2/CH2Cl2
N.R.
dark

Br2/CH2Cl2 Br
light + HBr

Br2/CH2Cl2 Br
light or Br + H2
dark
Br2/CH2Cl2
N.R
light or
dark
 Br Br
Br2/CCl4
H-C = C-H H- C = C - H
light or dark Br2/CCl4;ligh
t or dark
Br
H -Br
C-C-H
Br Br
3. Reaction with Baeyer’s rgt and Ammoniacal
AgNO3

Sample KMnO4 (cold,dilute.neutral) Ag(NH3)2+

Cyclohexane - -
Cyclohexene + -
Benzene - -
Reactions Involved:

KMnO4 N.R
H2O
KMnO4 OH
+ MnO2 + KOH
H2O OH

KMnO4, H2O N.R

 O
KMnO4, H2O
H-C=C-H H3C-C-OH + MnO2
+KOH
Ag(NH3)2+ H-C=C-Ag+ +NH3+NH4+

4. Preparation of Acetylene gas

CaC2 + 2H2O C2H2 (g) + Ca(OH)2
RELATIVE BROMINATION RATES OF
BENZENE AND SUBSTITUTED BENZENES
EXERCISE 7
MECHANISM OF ELECTROPHILIC
AROMATIC SUBSTITUTION
+
E E E E
H H H

With a substituent group G

G G G G
+
E E E E
H H H
Substituted rings are divided into two groups based
on the type of the substituent that the ring carries:

1. Activated rings: the substituent on the ring are

groups that donate electrons (activators). 

-NH2, -NR2 > -OH, -OR>  -NHCOR> -CH3 and other

alkyl groups

2. Deactivated rings: the substituent on the ring are

groups that withdraw electrons(deactivators).

-NO2, -CF3 > -COR, -CN, -CO2R, -SO3H > Halogens

Halogens: F> Cl > Br > I

ACTIVITY:

1.Observe the relative bromination rate of

substituted benzene
2.Compare bromination rates of the given
compounds
3.Make a relative classification of the
substituent group as ring activating or
deactivating based on experimental
observations