EXPERIMENT 5: ALCOHOLS AND PHENOLS

Eden Cabana, Nia Dominguez, Philip Gabriel Gimotea

Locker No. 21
Chemistry Department, Xavier University-Ateneo de Cagayan, Cagayan de Oro City
Date Performed: December 15,2014
Date Submitted: December 18, 2014

ABSTRACT
A functional group is an atom or group of atoms, bonded together in a certain
way, that as part of a molecule, will impart certain physical and chemical
characteristics to the molecule as a whole. It is the case that the rest of the
molecule can modify the characteristics of the functional group. It is also the case
that if the rest of the molecule is an alkyl group the modifications may be modest.
On the other hand, other functional groups in the molecule, especially if they are
close by, are more likely to profoundly modify the characteristics of the functional
group in question. Qualitative analyses of the different types of alcohols and
phenols were carried out. In the majority of experiment, four test samples were
used namely: ethanol, isopropyl alcohol, tertiary butyl alcohol, and phenol. With
these, the objectives of the experiment are to make an analysis of different types
of alcohols and phenols using different methods namely: the use of sodium
metal for the detection of acidic hydrogen in alcohols, the comparison of
oxidizing conditions of a compound using different solutions, the comparison of
oxidation rates of the different types of alcohols using one medium test, the
comparison of the relative acidity of phenol with other compounds, and phenol
reaction with bromine water; identify 1, 2 and 3 alcohols; and distinguish
alcohols and phenols from other compounds. In each test, different samples were
used and each of their reaction was observed for any indications of a positive test.
These can be helpful in analyzing and identifying unknown compounds by
analyzing their properties. In some tests, several compounds experienced side
reactions due to contamination, unclean equipment, and poorly prepared reagents
that might have been stored for a long time already. Moreover, most of the tests
had limitations.

INTRODUCTION

MATERIALS AND METHODS

Apparatus
1) 25mL test tube
2) Lighter
3) Asbestos mat
1

4) Mat
5) Iron stand
6) Iron ring
7) Beaker
8) Bunsen burner
9) Wire gauze
10)
Test tube holder
11)
1 Test tube rack
12)
2 Stirring rod
Chemicals
1) Small clean piece of 2mm cube metallic sodium; Na
2) 9 drops and 2 mL of anhydrous ethyl alcohol; C2H5OH
3) 10mL distilled water; HO
4) Blue litmus paper
5) Red litmus paper
6) 6 drops of 0.0002M KMnO
7) 8M NaOH
8) 3mL concentrated HCl
9) 1 mL isopropyl alcohol; CHO
10)
1 mL tertiary butyl alcohol; 2-methyl2-propanol
11)
5 drops of KCrO
12)
1 drop of 6M sulfuric acid; HSO
13)
1mL of 2% solution of phenol; CHO
14)
3mL sodium carbonate; NaCO
15)
1mL 1% acetic acid; CHO
16)
1mL 1-butanol
Procedure
A. Test for Acid Hydrogen in Alcohol
Precaution: Sodium is highly reactive and should not be held with bare
hands or be exposed to moisture
Drop a small clean piece of metallic sodium (2mm cube) into a previously
dried test tube containing 1mL of the anhydrous ethyl alcohol and immediately
observe what happens after. List down the observations and write the equation
that represents the reaction as Reaction 1a. Evaporate to dryness (in a water
bath) after the reaction has ceased. Cool, add 1mL of distilled water and test the
solution with litmus paper. Give a description and write the equation that
represents the reaction as Reaction 1b. Interpret the results by answering these
questions:
a)
What is the role of sodium metal in this procedure?
b)
What does the reaction of ethanol with sodium tell you about the
acidity of
alcohols?
c)
What property of alkoxide ions is exhibited in the experiment?
B. Comparison of Oxidizing Conditions
Set 3 test tubes in a rack. To each test tube, place 3 drops of ethyl alcohol,
3mL of water and 2 drops of 0.0002 KMnO solution (just enough to give the
solution a pink color). Simultaneously place in test tube #2, a stirring rod which
has just been dipped in 8M NaOH solution and in test tube #3, a stirring rod
2

which has just been dipped in concentrated HCl. In which medium was the
oxidzation (evidenced by decolorization) most rapid: acidic, basic, or neutral? For
the relative ease of oxidation, write 1= fast, 2=moderate, 3=slow. Provide an
explanation for the differences in the rate of reaction.
C. Comparison of Oxidation Rate of 1, 2 and 3 alcohols
Set 3 test tubes in a rack. Put mL of ethyl alcohol in the first test tube,
mL isopropyl alcohol in the 2 nd test tube and tertiary butyl alcohol in the
third test tube. To each, add 5 drops of 0.017M KCrO and 1 drop of 6M sulfuric
acid solution. Warm. Note the color and odor of the solutions. Compare the ease
by which each of the alcohols is oxidized. For the relative ease of oxidation, write
1=fast, 2=moderate, 3=slow. Provide an explanation for the differences in the
rate of reaction.
D. Comparison of the Rate of Substitution or Lucas Test
This test is used to distinguish among primary, secondary, and tertiary
water soluble alcohols. Into 3 separate test tubes, transfer 1 mL each ethyl
alcohol, isopropyl alcohol and tertiary butyl alcohol. Add an equal amount of
concentrated HCl to each. Shake for a few minutes at room temperature and
allow to stand. Observe closely. Compare & account for the difference in the rate
of reaction of these alcohols. For the relative ease of substitution, write 1=fast,
2=moderate, 3=slow. Take note of the alcohol which gives a surface layer of the
alkyl chloride.

E. Acidity of Phenol
Mix 1mL of a 2% solution of phenol with 1mL of a sodium carbonate
solution. Note if carbon dioxide is evolved. Repeat the test using 1% solution of
acetic acid and 1-butanol in 2 separate test tubes instead of phenol as the acid.
Add 1mL of sodium carbonate solution to each. Compare the acidity of phenol to
acetic acid and 1-butanol based on the rate of reaction with sodium carbonate
solution and account for the difference.
F. Reaction of Phenol with Bromine Water
Add bromine water dropwise to 5 drops of the phenol solution. What is the
solid so readily precipitated? Is phenol easier or more difficult to substitute with
bromine than benzene? Give a chemical explanation in support of the choice
made.

RESULTS AND DISCUSSION

Table 1. Test for acidity in alcohol
Step

After dropping Na to
ethanol

Description

Na dissolves in ethyl alcohol with the presence

of bubbles. The test tube also became hot.
3

Chem
Reacti
on
1a

After evaporation of
There is a presence of white residue
solution
After addition of water &
The outer surface of the test tube was hot. The
after testing the solution
red litmus paper turned blue while there were
w/ litmus paper
no changes in the blue litmus paper.
Chemical Equations:
1 2 C2H5OH + 2 Na = 2 C2H5ONa + H2
a
1
b

1b

For the test of acidity in alcohol, several bubbles are arising from the water surface
because it indicates the presence of sodium which is highly relative. The role of the
metal in this procedure is to distinguish the acid hydrogen from the used alcohol.
Litmus paper was then used to test the solution. It is when it identifies the acidity of
the compound in every procedure. The acidity of alcohols in the reaction of ethanol
with sodium doesn't require much phenol since it is a weak acid that leads the
experiment into slow reaction. It is not directly able to react because of its acid.
There is some fizzing as hydro gas is given off. The mixture left in the tube will
contain sodium phenoxide.
Table 2. Comparison of oxidizing conditions
Alcohol
+
Description
Relative Chem.
KMnO
Ease of
Reacti
Oxidation
on
Ethanol
+ First, there were two layers the lower clear 3
2a
KMnO
part and the pink upper part. After a few
(neutral
minutes, the upper part became darker.
medium)
Ethanol
+ First, there were two layers the lower clear 1
2b
KMnO
+ part and the light green upper part. After a
NaOH
few minutes, the upper part became yellow.
Ethanol
+ First, there were two layers the lower clear 2
2c
KMnO + HCl
part and the pink upper part. After a few
minutes, the whole mixture became clear.
Chemical Equations:
2 CHCHOH + KMnO = CHCOOH + HO + MnO + K
a
2 CHCHOH + KMnO + NaOH = MnO + CHCOONa + 2 HO + K
b
2 CHCHOH + KMnO + HCl = CHCOOH + MnO + HO + 2 KCl
c
In comparing the oxidation of ethanol with potassium permanganate in solutions of
different acidities, it was observed that oxidation was fastest in the basic medium
(NaOH) rather than the acidic one (H 2SO4). Oxidation of ethanol and the reduction of
potassium permanganate in H2SO4 produced acetic acid and Mn 2+, which gave the
pale pink color of the solution. On the other hand, the production of MnO 2 together
4

with acetic acid from the reaction of ethanol in a NaOH solution resulted in
the green color of the solution. Oxidation did not happen in water since it is a
neutral solution and did not cause redox reactions.
Table 3. Comparison of Oxidation Rate of 1, 2, 3 Alcohols
Alcohol +
Description
Relative Chem.
Acidic KCrO
Ease of
Reacti
Oxidation
on
Primary
alcohol
Aqueous mixture with a formation of 2
1
3a
used
layers; yellow above a white liquid
(C2H5OH)
Secondary Alcohol Homogenous aqueous transparent-white
2
3b
used
colored mixture
( CHO )
Tertiary
Alcohol
Homogenous aqueous clear yellow
3
3c
used
mixture
( 2-methyl2propanol )
Chemical Equations:
3 KCrO + HSO + CHO = Cr (SO) + CO + KSO + HO + CHO
a
3 5 C3H8O + K2Cr2O7 + 4 H2SO4 = Cr2(SO4)3 + K2SO2 + 5 CH3CH2CHO + 9 H2O
b
3 26 C4H10O + K2Cr2O7 + 2 H2SO4 = 26 C4H9O + 2 KCrS + 15 H2O
c
Oxidation mechanism of alcohols is different for different types of alcohols. Primary
alcohols can be oxidized to either aldehydes or carboxylic acids depending on the
reaction conditions. In the case of the formation of carboxylic acids, the alcohol is
first oxidized to an aldehyde which is then oxidized further to the acid. Secondary
alcohols are oxidized to ketones - and that's it. For example, if you heat the
secondary alcohol propan-2-ol with potassium dichromate(VI) solution acidified with
dilute sulfuric acid, you get propanone formed. Tertiary alcohols aren't oxidised by
acidified sodium or potassium dichromate(VI) solution. There is no reaction
whatsoever. If you look at what is happening with primary and secondary alcohols,
you will see that the oxidizing agent is removing the hydrogen from the -OH group,
and a hydrogen from the carbon atom attached to the -OH. Tertiary alcohols don't
have a hydrogen atom attached to that carbon.
Table 4. Comparison of Rate of Substitution of Alcohol (Lucas Test)
Description
Relative
Alcohol + Conc.
Ease of
HCl
Substitut
ion
Primary Alcohol
(C2H5OH)
5

Chem.
Reacti
on
4a

Secondary Alcohol
( CHO )
Tertiary Alcohol
( 2-methyl2propanol )
Chemical Equations:
4 C2H5OH + HCl = C2H5Cl + H2O
a
4 C3H7OH + HCl = C3H7Cl + H2O
b
4 C4H10O + HCl = C4H9Cl + H2O
c

4b
4c

Lucas test is used to classify and distinguish alcohols as primary, secondary, or

tertiary alcohols. It is based on the difference in reactivity of the three classes of
alcohols with hydrogen halides. In Lucas test, the formation of two layers (aqueous
layer and cloudy layer) is known as a positive test. The second layer (cloudy layer)
formed is alkyl chloride which is insoluble in the aqueous solution because all the
alkyl halides molecules are insoluble in the water. The alkyl chloride produced from
the reaction is not water-soluble and causes cloudiness (emulsion) to form in the
aqueous solution. For all the alcohols, it does not react appreciably with Lucas
reagent at room temperature especially with ethyl. It was observed to be the fastest
to give the rate because it involves the transformation of carbohydrates in which
the reaction of the alcohol is determined by the ease of formation of the
carbonation. In isopropyl alcohol, what causes to take more than a minute or a slow
reaction is its solubility with the reagent while in tertiary butyl alcohol, it react
immediately by which it is called to be the turbidity, owing to the low solubility of
the organic chloride in the aqueous mixture or liquid mixture. The reaction that
takes place on the Lucas test is a SN1 nucleophilic substitution. The alcohols with
the properties of generating a stable carbocation intermediates will undergo the
particular reaction. The OH group of the alcohol attracts the H in hydrochloric acid
to form oxonium ion and leave the group (form water). The carbocation
intermediate is formed and tends to react with Cl- (nucleophile) to produce the alkyl
halide product. http://1chemistry.blogspot.com/2011/05/properties-of-alcohol.html
Table 5. Relative Acidity of Phenol
Chem. Family/
Description
Chem.
Name of
Reacti
Compound
on
Tested
Phenol
5a
( C6H6O )
Alcohol used
5b
( C2H4O2 )
Carboxylic Acid
5c
used
Chemical Equations:
6

5 2 C6H6O + Na2CO3 = 2 NaOH + 2 C6H5 + CO3

a
5 Na2CO3 + 2 C2H4O2 = CO2 + H2O + 2 NaC2H3O2
b
5
c
Compounds like alcohols and phenol which contain an -OH group attached to a
hydrocarbon are very weak acids. However, phenol is sufficiently acidic for it to
have recognizably acidic properties - even if it is still a very weak acid. A hydrogen
ion can break away from the -OH group and transfer to a base. Phenol is not acidic
enough to react with sodium bicarbonate or the carbonate and hydrogencarbonate
ions are not strong enough bases to take a hydrogen ion from the phenol. Unlike the
majority of acids, phenol does not give carbon dioxide when you mix it with sodium
bicarbonate. You can recognize phenol because it is fairly insoluble in water, it
reacts with sodium hydroxide solution to give a colorless solution, and it does not
react with sodium carbonate or hydrogencarbonate solutions. Carboxylic acids are
usually stronger acids than phenols and phenols are stronger acids than alcohols.
Thus, phenol is more acidic than 1-butanol and less acidic than acetic acid. Electron
withdrawing groups, like nitro, will increase the acidity of phenols and carboxylic
acids because they stabilize the phenoxide and carboxylate anions that are
produced as the acid gives up its proton
Table 6. Reactivity of Phenol with Bromine Water
Reactions
Description

Chem.
Reacti
on
6a

EAS halogenations
without Lewis acid
as catalyst
Chemical Equations:
6 BrHO + CHO = CH + HO + BrO
a
When adding bromine water to a solution of phenol in water, the bromine water is
decolorized and a white precipitate is formed which smells of antiseptic. The
precipitate is 2,4,6-tribromophenol. Unlike other arenes, the benzene ring in phenol
is about 100 times more reactive in benzene itself, because of the hydroxyl group
attached to it. Therefore, phenol does decolorize bromine water, though it still
undergoes a substitution reaction.
http://www.chemistryrules.me.uk/candrands/arenes.htm
CONCLUSION
REFERENCES: