ALCOHOLS, PHENOLS AND ETHERS

J.V. DE GUZMAN
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: FEBRUARY 27, 2015
INSTRUCTORS NAME: ALLAN KENNETH REGUNTON

ANSWERS TO QUESTIONS
1. Give the balance equations for all the reactions.
a. Ethyl alcohol + Lucas Reagent
ZnCl2

+ HCl
No reaction (clear, colorless solution)
b. Isopropyl Alcohol + Lucas Reagent
ZnCl2

+ HCl

+ H2O
(slow)

Insolule-cloudiness

c. Benzyl alcohol + Lucas Reagent

ZnCl

+ HCl

+HO

Insolule-cloudiness
2

d. Tert-butyl alcohol + Lucas Reagent

ZnCl
2

+ HCl
e. Ethyl alcohol + KMnO4

Insolule-cloudiness

+ MnO4Balanced:
CH3-CH2-OH +
COH=O +
H2O
f. Isopropyl alcohol + KMnO4

+ MnO4-

+ H2O

+ MnO4MnO4-(aq)

(fast)

MnO2(s) +

+ MnO2(s) + 2H2O

+ MnO2(s)
CH3-

g. Benzyl alcohol + KMnO4

+ MnO4h. Tert-butyl alcohol + KMnO4

+ MnO4i. Diethyl ether + KMnO4

+ MnO2(s) + H2O

No Reaction

+ MnO4j. Phenol + Bromine water

No Reaction

+ 3Br2
k. Phenol + KMnO4

+ 3HBr

+ MnO4l. Phenol + FeCl3

36
+ FeCl3
+ 3Clm. p-nitrophenol + FeCl3

3
+ FeCl3
HCl
n. p-bromophenol + FeCl3

3
+ 3HCl

+ FeCl3

Fe

+ 6H+

Fe

Fe

o. -naphthol + FeCl3

+ FeCl3
3

Fe

+ 3HCl

2. Why is Lucas Test applicable only to alcohols containing 5 or

less carbons?
Lucas test makes use of the solubility of the reagent for the reaction to
happen. As such, this method applies only for alcohols that are soluble
in the reagent in order for the chlorination reaction of the alcohol to
occur. Lucas reagent is a solution of ZnCl 2 in HCl, as such; this polar
solution dissolves only highly polar alcohols or those that have less
number of non-polar groups. More than 5 carbons, the alcohol becomes
more nonpolar, therefore, Lucas test is applicable only to alcohols with
less than 5 or less carbons.
3. Why tertiary alcohols and ethers cannot undergo oxidation
upon reaction with potassium permanganate?
Oxidation of the alcohol depends on its relative stability. As the number
of alkyl substituent of the carbon of which the hydroxide is bonded
increases, the greater is the stability of the alcohol. Therefore, it can be
arranged that tertiary alcohol>secondary alcohol>primary alcohol in
terms of stability. Permanganate can oxidize primary alcohols into
aldehyde then into carboxylic acids and secondary alcohols into
ketones only. However, potassium permanganate cannot remove an
electron from a tertiary alcohol to oxidize it because of its great
stability. The same also applies for diethyl ether. The symmetric
structure of diethyl ether gives stability to the molecule as such
permanganate cannot withdraw an electron form it.
4. Correlate the structure of the phenolic compounds with the measured
pH values.
Given are the structure and corresponding pH values of phenolic
compounds:

Picric acid (pH=3)

p-nitrophenol

Phenol (pH=5)

The relative acidity of phenolic compounds is dependent on electron

withdrawing groups attach to the ring. As the electron withdrawing group
increases, the benzene ring becomes more positively charged thereby
making the compound more acidic. In phenol, there is only one electron (OH) withdrawing group and two for p-nitrophenol (-OH and NO2) making
nitrophenol more acidic than phenol. Picric acid has four electron
withdrawing groups (-OH and 3(-NO2)) making it the strongest organic acid.
This idea correlates with the obtained pH values of the phenolic compounds:
picric acid > p-nitrophenol > phenol in terms of relative acidity.
REFERENCES:
[1]Pahlavan, L. Properties of Alcohol: structure, reactions and identification
of alcohols. Southwest College Houston Community College. [Online].
2014. Retrieved from: http://swc2.hccs.edu/pahlavan/2425L4.pdf
(accessed March 3, 2015).
[2]Pavia, D. L., Lampman, G. M., Kriz, G.S., Engel, R. Introduction to Organic
Laboratory Techniques: A Microscale Approach. Part 3: Identification of
Organic Substances-Experiment 53H: Alcohols. Saunders College
Publishing: Orlando, 1995. pg 513.
[3]Xiamen University. Oxidation of Alcohols. [Online]. 2002. Retrieved from:
http://chem.xmu.edu.cn/teach/yjhx/chem/02en/chpt12_2.pdf (accessed
March 3, 2015).