Alcohols

and Phenols
Acosta, Dianne Mae; Allawan, Giovanni; Mina, Leica
Department of Physical Sciences, College of Science, UP Baguio, Baguio City 2600
Performed 25 September 2019; Submitted 4 October 2019

ABSTRACT

Alcohols and phenols are organic compounds that have a hydroxyl group (OH) attached to a saturated or an
aryl carbon, respectively. Alcohols are weak acid compared to phenols since phenols act as a weak acid in water.
The alcohol can further be classified as primary, secondary or tertiary depending on the location of the hydroxyl
group. For phenol, it is composed of a benzene ring with an -OH group attached to it. The OH group is
responsible for the compounds’ varying physical and chemical properties. These properties were determined
using various tests. For the physical property, solubilities of alcohol and phenol in water were tested wherein
only ethanol, n- butyl alcohol, sec-butyl alcohol, phenol and benzyl alcohol were soluble. Tests for chemical
properties were also tested by observing their reactions with various reagents. Phenol and ethanol tested both
positive for esterification. Moreover, alcohol n-butyl and tert-butyl were positive for the Lucas test. For the
oxidation of the OH group, alcohol representatives n-butyl, sec-butyl and tert-butyl alcohol tested positive. The
iodoform test for ethanol also tested positive because of the formation of a yellow precipitate. Lastly, the phenol
reacted with the Br water since the Br water was decolorized. For the test for the enol group and the test with
the aqueous neutral KMnO4, phenol showed positive results in the form of a color change.

Introduction To distinguish different classes of phenols and

alcohols, these compounds can be tested with
An alcohol is an organic compound which has a various reagents and methods. Lucas Test, a
hydroxyl group (-OH) attached to a carbon atom. method used to determine whether an alcohol is
This carbon atom should be saturated which primary, secondary or tertiary by their rate of layer
basically means that it single bonded to hydroxyl formation using anhydrous zinc chloride in
functional group and other three atoms, similar to concentrated hydrochloric. Generally, primary
phenols (McMurry, 2003). Both these compounds alcohols obtain a clear homogeneous solution. On
are weakly acidic and weakly basic like water and the other hand, secondary alcohols form two layers
as Lewis bases, strong acids reversibly protonate after a few minutes, and tertiary alcohols form two
alcohols and phenols to generate oxonium ions, distinguishable layers immediately (Ahluwalia &
ROH:2+(McMurry, 2003). According to Smutek, et Dhingra, 2004).
al. in 2012, alcohols and phenols as weak acids
donate a proton to water resulting them to Secondly, alcohols can also be categorized based on
dissociate in dilute aqueous solution, yielding their reaction with oxidizing agents particularly
H3O+and an alkoxide ion (RO-) or a phenoxide ion potassium dichromate, chromic acid and
(ArO-). potassium permanganate. Primary alcohols oxidize
into aldehydes, secondary alcohols form ketones
Alcohols can be classified into primary (1°), with oxidation to chromic acids, while tertiary
secondary (2°) and tertiary (3°) alcohols according alcohols do not undergo oxidation in such
to the number of alkyl groups bonded to the carbon conditions since all attachments of carbon are
atom that has the –OH group attached (Shriner, already occupied by three R groups, leaving no
2004). In 1° alcohols, the –OH group is bonded to a attachment for a hydrogen atom that can be
carbon atom with one or no alkyl groups attached. attacked by oxidizing agents (Hirano et al., 2008).
In 2° alcohols, the –OH group is bonded to a carbon
atom with two alkyl groups attached. In 3° alcohols, The experiment aims to test and compare the
the –OH group is bonded to a carbon atom with physical and chemical properties of alcohols and
three alkyl groups attached (Shriner, 2004). phenols by observing their solubilities in water and
their chemical reactions with different reagents.
Experimental Method 2.00 mL of H2O and 2.00 mL of 6 M NaOH were
added to 10 drops of ethyl alcohol then mixed and
A. Solubility in H2O warmed in 60-degree Celsius water bath. I2-KI
reagent was added dropwise until the solution
0.50 mL each of ethyl alcohol, n-butyl alcohol, sec-
becomes brown or yellowish for two minutes then
butyl alcohol, tert-butyl alcohol, benzyl alcohol,
added with 6 M NaOH dropwise until colorless. The
glycerol and 0.50 g each of phenol, p-nitrophenol,
mixture was set aside for 15 minutes then
and p-methylphenol in seven separate test tubes
observed for formation of yellow precipitate.
were each added with 1 mL of water then shaken.
Water was added dropwise to cloudy solutions C. Reactions of Phenol
until a homogeneous mixture was obtained, noting
the total volume added. Solutions were recorded 1. Reaction with Br2 in H2O
soluble if no cloudiness appears upon adding 2.00
A solution of 1.00 mL H20 and few crystals of
mL of water.
phenol was warmed in a 60-degree Celsius water
B. Reactions of the OH Group bath then cooled and added with Br2 in H2O
dropwise.
1. Reaction with metal
2. Test for the enol group in phenols
One small sodium pellet was each added to 0.50
mL-n-butyl alcohol, sec-butyl alcohol, tert-butyl Three drops of ethyl alcohol and a phenol crystal
alcohol, and 0.50-g phenol in four separate test was each added to five drops of 10% FeCl3 solution
tubes, then compared for their gas evolution rates. in two separate test tubes then compared for the
Unreacted sodium metal was completely dissolved results.
in ethyl alcohol to avoid violent reactions with
3. Reaction with aqueous neutral KMnO4
water.
Few phenol crystals were dissolved in 10 drops of
2. Reaction with acid
H20, added with two drops of aqueous neutral
Five drops of ethyl alcohol, five drops of glacial KMnO4, then observed for the decolorization of
acetic acid, and one drop of concentrated H2SO4 KMnO4.
were combined in a test tube and warmed on low

flame then noted for the odor of the product. The
same procedure was performed using five drops of
phenol.

3. Lucas Test

3.00 mL of Lucas reagent was each added to 10
drops of n-butyl alcohol, sec-butyl alcohol, and tert-
butyl alcohol in three separate test tubes, then
mixed well and allowed to stand for five minutes,
observing for any cloudiness. The mixtures were
warmed in a 60-degree Celsius water bath for 15
minutes when there was no cloudiness after 10
minutes then recorded for observations.

4. Oxidation

10 drops of dilute H2SO4 and two drops of 10%
K2Cr2O7 solution were added to five drops of n-
butyl alcohol and warmed gently then noted for the
color and odor of the solution. The procedure was
repeated using sec-butyl alcohol and tert-butyl
alcohol.

5. Iodoform Test

Results and Discussion with an -OH group attached to it, is also soluble in
water since it is a weak acid and is able to form
Solubility test in water strong hydrogen bonds with water molecules,
forming a phenoxide ion in the process (Solomons
Table 1. Solubility test in water of et. al, 2014; Stoker, 2013). P-nitrophenol is soluble
alcohols and phenols in water since it is slightly acidic than water with a
Volu pKa of 7.15 (Solomons et. al., 2014) and thus it
me of dissociates in water.
Test H2O Solubil
Observation
compound adde ity Tert-butyl alcohol, benzyl alcohol, glycerol, p-
d nitrophenol, and p-methylphenol were insoluble in
(mL) water. Tert-butyl alcohol has three carbon
Particles at containing atoms attached to the bonded carbon
Ethyl 0.25 mL, clear 0.75 and -OH group. Generally, alcohols are polar
+
alcohol solution at 0.75 mL because of the -OH group attached to their carbon
mL and should be able to bond with water molecules
Cloudy solution through hydrogen bonding (Brown et. al., 2014),
n-butyl 2.00 but since the tert-butyl alcohol and water solution
at 1.0 mL, +
alcohol mL was still cloudy after 2.00 mL drops of water, it was
colloidal layer
Cloudy solution observed to be insoluble. Benzyl alcohol was
Sec-butyl 1.75 insoluble in water because it is a nonpolar
at 0.50 mL, +
alcohol mL compound, naturally not being able to react with
colloidal layer
Cloudy solution water. The presence of three hydroxyl groups in
Tert-butyl 2.00 glycerol, should allow it to be soluble in water, but
at 0.50 mL, two -
alcohol mL cloudiness persisted after addition of 2.00 mL of
layers
Cloudy solution water. Therefore, glycerol was observed to be
Benzyl 0.50 insoluble in water. P-methylphenol was also
with -
alcohol mL observed to be insoluble since it produced a cloudy
effervescence
2.00 solution as seen in figure 1 below. Ideally, P-
Glycerol Two layers - methylphenol (or p-cresol) has a higher pKa value
mL
Cloudy solution of 10.17 (Solomons et. al., 2014) meaning it is a
(salmon), 0.25 weaker acid compared to p-nitrophenol, and since
Phenol + water is a stronger base in this case, it does not
effervescence mL
top layer dissociate completely.
Crystals settle
p-
at bottom with 2.00
nitrophen +
a bit floating on mL
ol
the top layer
Bubbles at 1.00
p-
mL, 2.00
methylphe -
bubbles/precip mL
nol
itate settled

The following alcohols and phenols were tested for

their solubility in water by observing their mixture
with water; if cloudiness persisted after addition of
2.00 mL water, the compound is insoluble. From
the table above, ethyl, n-butyl, and sec-butyl
alcohols are soluble in water since only one Figure 1. (from left to right) p-methylphenol with
hydroxyl (-OH) group is present in their structure water and p-nitrophenol with water.
and they contain not more than five carbon atoms
(Henrickson et. al., 2001). Phenol, an aromatic ring OH reaction with Na metal
 acid + produced
Table 2. Reaction of OH with a metal concentrated white gas,
Test sulfuric acid sweet smell
Observations Rank
compound Phenol + Light
Fast rate of glacial acetic purple/dark
n-butyl
bubbles 2 acid + pink to brown +
alcohol
forming concentrated solution, sour
Fast rate of sulfuric acid smell
Sec-butyl
bubbles 1
alcohol
forming Both alcohols, ethyl alcohol and phenol, exhibited
Slow positive results for esterification. For ethyl alcohol,
Tert-butyl
continuous 3 white gas and a sweet odor were produced due to
alcohol
bubbles the ester product or ethyl acetate. The figure below
phenol No bubbles 4 shows the esterification of ethyl alcohol. The -OH
group from the glacial acetic acid protonates one H
The test compounds n-butyl alcohol, sec-butyl atom from the ethyl alcohol to form H2O as a
alcohol, tert-butyl alcohol, and phenol were tested byproduct.
with Na metal. These are weak acids, but they could
still donate the hydrogen from their hydroxyl
group. Through observation, the gas formation of
phenol was persistent yet milder than the
formation of bubbles on the other three test
compounds. This was the reason it was ranked 4th
when comparing the rate of the bubbles.
Supposedly, phenol should have been ranked 1st
since it is the most acidic having a pKa of 10 while
the alcohol test compounds have a pKa of 16-18

(Sparkman, Penton, & Kitson, 2011). Acids are
Figure 2. Esterification of Ethyl Alcohol.
more reactive when introduced to Na metals since

they are good reducing reagents, thus the stronger
For phenol, the color of the solution changed from
the acid the greater its reactivity (Likens & Butler,
light purple to brown. Moreover, a sour smell was
2018). Due to the increase in electron density of
also observed. Phenols are less reactive with glacial
oxygen and steric hindrance, phenol is followed by
acetic acid compared to ethyl alcohol. Thus, the
tert-butyl alcohol, n-butyl alcohol, and sec-butyl
esters or the phenylacetate that were produced are
alcohol in terms of rate of gas evolution.
smaller and has a different odor compared to the

ethanol.
OH reaction with an acid


Lucas test
Esterification is the reaction that takes place when

alcohols and carboxylic acids make esters. These
Table 4. Lucas Test
are produced when the alcohol is heated in the
Test
presence of an acid catalyst (Clark, 2015). In this Observations Cloudiness
compound
experiment, the alcohols that were tested were
ethyl alcohol and phenol. Glacial acetic acid was Cloudiness
the carboxylic acid utilized while the concentrated formed after
n-butyl +
sulfuric acid served as the acid catalyst. The table heating at 14
below shows the observations and the reaction minutes
mixture. Cloudiness
formed but
Sec-butyl -
Table 3. Reaction of OH with an acid the solution
Reaction becomes clear
Observations Esterification Produced
mixture
colorless
Ethyl alcohol Colorless Tert-butyl +
+ solution at 1
+ glacial acetic solution,
minute

As for the Lucas test, n-butyl and tert-butyl alcohol
showed positive results. N-butyl alcohol at first did
not react or showed any pertinent response
however, when it was heated to a water bath for
about 14 minutes, the solution started to be cloudy.
Tert-butyl on the other hand exhibited cloudiness
after shaking for a few minutes. The reaction that
occurred in Lucas test is nucleophilic substitution.
In particular, the cloudiness was a result of the
formation of alkyl chloride as seen in the equation
below. The reaction between tert-butyl alcohol and
Lucas reagent was made possible by the 3 alkyl
groups attached to tert-butyl alcohol reacting to

the reagent explaining the immediate cloudiness Figure 3. (from left to right) n-butyl alcohol, sec-
formed when they were mixed. N-butyl reaction butyl alcohol, and tert-butyl alcohol after addition
only occurred when it was placed in a water bath of dilute H2SO4 and 10% K2Cr2O7 and heated.
mainly because of the heat acted on the solution
making the reaction faster since they are exposed In general, primary alcohols oxidize to an aldehyde
to a harsher environmental condition thus allowing first then hydration will occur in which the
the nucleophilic substitution to occur. On the other aldehyde hydrate formed by the addition of a water
hand, sec-butyl did not react with Lucas reagent molecule to the aldehyde group will then form two
since no cloudiness was formed in the solution. hydroxyl groups; the chromic acid will react with
Yielding this result is very common among one of the -OH groups and complete oxidation, thus
experimenters since the formation of cloudiness is becoming a carboxylic acid (Solomons et. al., 2014;
affected by different factors such as swirling, or the McMurry et. al. 2016,; Brown et. al., 2014; Stoker,
amount of alcohol placed in the solution. 2013). As seen in figure 4, n-butyl alcohol or n-
butanol oxidized to butyraldehyde by elimination
ROH + HCl → RCl + H2O
of two hydrogen atoms. Hydration then forms the
hydrate which then oxidizes to become butyric
Oxidation of -OH group acid.

Table 5. Oxidation of OH group.
Test
Observations Color change Figure 4. Oxidation of n-butyl alcohol.
compound
n-butyl Green color,
+ Secondary alcohols produce ketones and also
alcohol sweet odor
Blue-green involves the elimination of two hydrogen atoms.
Sec-butyl Figure 5 shows sec-butyl oxidizing into a ketone
color, sweet +
alcohol with water as a by-product.
odor
Tert-butyl Green color,
+
alcohol strong odor

For the oxidation of the hydroxyl group, dilute
sulfuric acid (H2SO4) and 10% potassium
dichromate (K2Cr2O7) were used to form chromic Figure 5. Oxidation of sec-butyl alcohol.
acid (H2CrO4) as a reagent for testing the oxidation
of the hydroxyl group in the three test compounds. Tert-butyl does not oxidize because the carbon
After adding the reagent, the test compounds were with the -OH group is bonded to three carbons and
heated at minimal heat and produced a color cannot form additional C-O bond (Brown et. al.,
change from yellow to a blue-green or green color. 2014). However, a color change in the solution was
still observed.

Iodoform test
 Phenol: dark
The iodoform test is performed in order to Test for enol color, two Phenol (+)
determine if there is a presence of the CH3CH(OH) group in layers Ethyl alcohol
group or triiodomethane in alcohols. Specifically, phenols Ethyl OH: no (-)
this test was conducted for ethyl alcohol, the only color change
primary alcohol that can give a positive result for Color of
the iodoform test. The formation of a yellow solution was
precipitate as seen in the figure below confirms the Reaction with
dark brown
aqueous
presence of triiodomethane or iodoform in ethanol. and +
On the other hand, most secondary alcohols yield neutral
precipitate
positive results because of their methyl group KMnO4
settled
attached to a carbon with an -OH group. However, afterwards
tertiary alcohols yield negative results for the
iodoform test (Clark, 2004). The reaction of phenol with bromine in water (Br2
H2O) produced two layers with small bubbles
visible and decolorizing the solution. The bromine
reacted with the phenol through bromination in
electrophilic aromatic substitution (Solomons et.
al., 2014).

Figure 8. Reaction of phenol and bromine in
aqueous solution.
Figure 6. Formation of triiodomethane.
Phenol reacted to the iron chloride (FeCl3) rapidly
The first step involved the substitution of all three and produced a black color and forming two layers
hydrogens in the methyl group by the iodine ions. in the mixture, while the ethyl alcohol did not react
For the second step, the bond between the CI3 and to the FeCl3, making the FeCl3 retain its color. The
the rest of the molecule were broken. This results addition of FeCl3 serves as a color test for phenols
to the formation of triiodomethane or iodoform in which their color can vary from green to purple
and the salt of an acid (Clark, 2004). The figure depending on their structure (Bettelheim &
below shows a summarized reaction of ethanol Landesberg, 2011). In this case, a dark purple color
under the iodoform test. was observed. The FeCl3 then forms a complex with
phenol, producing hydrochloric acid as a by-
product of the reaction.


Figure 7. Positive reaction of ethanol
in the iodoform test.

Phenol reactions

Table 6. Reactions of phenol
Test/action
Observations Color change
taken
Two layers
Reaction with (insoluble)
+
Br2 H2O with small
bubbles

Figure 12. Oxidation of phenol to p-quinone.

Conclusion and Recommendations

Alcohols have hydroxyl (-OH) groups attached to
their carbon and can be further classified as
primary, secondary, or tertiary alcohols. Phenol on
Figure 9. (from left to right) Phenol with FeCl3 and the other hand is an aromatic ring with an -OH
ethyl alcohol with FeCl3. group attached to it. The physical and chemical
properties of alcohols and phenols were tested by
subjecting respective alcohols and phenols in
reagents, and the -OH groups attached to these
carbon chains and rings will determine the
reaction of the compound.
Figure 10. Reaction of phenol with FeCl3.
For the solubility of alcohols and phenols in water,
The reaction of phenol with potassium ethanol, n-butyl alcohol, sec-butyl alcohol, benzyl
permanganate (KMnO4) produced dark brown alcohol, and phenol were soluble because of the
colored solution and precipitates settled at the hydrogen bonding formed by their respective -OH
bottom of the test tube afterwards. Phenols are groups with water molecules. Tert-butyl alcohol,
only oxidized by strong oxidizing reagents, and glycerol, p-nitrophenol, and p-methylphenol were
since KMnO4 is a strong oxidizing reagent, it insoluble in water. Tert-butyl alcohol and glycerol,
oxidized the -OH group attached to the benzene although capable of forming hydrogen bonding,
ring. As seen in figure, the phenol reacted with produced a cloudy solution and therefore was
KMnO4 to form hydroquinone which then turns observed to be insoluble in water. P-nitrophenol
into p-quinone. and p-methylphenol reacted with water as an acid;
p-nitrophenol slightly acidic than water and thus
dissociates, while P-methylphenol and it does not
dissociate completely in water.

For test on reaction with sodium metal, the tested
organic compounds are weak acids but are still
capable of donating the hydrogen atom from their
respective -OH group. Sec-butyl alcohol had the
fastest rate of bubble formation, followed by n-
butyl alcohol, tert-butyl alcohol, and phenol.
However, phenol should have reacted the fastest
with the sodium metal since it is the most acidic.

Ethyl alcohol and phenol had positive results for
esterification. For ethyl alcohol, the -OH group
Figure 11. Phenol reacted with KMnO4. from the glacial acetic acid protonates one H atom
from the ethyl alcohol, forming H2O as a byproduct
in the process. For phenol, smaller esters were
produced since they are less reactive with glacial
acetic acid than ethyl alcohol is.

For the Lucas test, n-butyl and tert-butyl alcohol Bettelheim, F.A. & Landesberg, J.M. (2013).
exhibited positive results. The three alkyl groups in Laboratory Experiments for Introduction
tert-butyl alcohol reacted with the Lucas reagent to General, Organic, and Biochemistry (8th
through a nucleophilic substitution reaction. As for ed.).
the n-butyl alcohol, the heat applied to the solution
made the reaction faster, allowing nucleophilic Brown, W. H., Iverson, B. L., Anslyn, E. V., & Foote,
substitution to occur. On the other hand, sec-butyl
C. S. (2014). Organic Chemistry (7th ed.).
did not react with Lucas reagent since no
cloudiness was formed in the solution. US: Brooks/Cole, Cengage Learning.

For the oxidation of the hydroxyl group, all the test Clayden, J., Greeves, N., & Warren, S. (2012).
compounds exhibited a color change. N-butyl Organic Chemistry (2nd ed.). US: Oxford University
oxidized to an aldehyde by elimination of two Press Inc., New York
hydrogen atoms, then its carboxylic acid is then
formed by the hydrate. Sec-butyl alcohol oxidized
Clark, J. (2004). Triiodomethane (iodoform)
into a ketone as it is a secondary alcohol. Tert-butyl
reaction with alcohols. Retrieved on 04
alcohol, having three carbons bonded to the carbon
September 2019 from http://www.ch
with the -OH group, does not oxidize. However, in
emguide.co.uk/organicprops/alcohols/
this experiment, a reaction was still observed.
iodoform.html.

The iodoform test was conducted for ethyl alcohol,
Clark, J. (2015), Esterification. Retrieved on 04
the only primary alcohol that can give a positive
September 2019 from www.chemguide.
result for the iodoform test. The substitution of all
co.uk/organicprops/alcohols/
three hydrogens in the methyl group by the iodine
esterification.html.
ions occurred in the first step, and the bond
between the CI3 and the rest of the molecule were
broken afterwards. Shriner, Hermann, Morill, et. Al. 2004. The
Systematic Identification of Organic
Phenol was reacted with different reagents to test Compounds. John Wiley and Sons Inc.USA.
for its chemical properties. When reacted with the
bromine in water solution, the Br2 was decolorized Henricksen, C.H., Byrd, L.C., & Hunter, N.W.
through an electrophilic aromatic substitution (2001). A Laboratory for General, Organic,
reaction. The test of phenol with FeCl3 produced a and Biochemistry (3rd ed.). New York, NY:
dark color, in which the FeCl3 formed a complex
McGraw-Hill.
with the phenol and forming hydrochloric acid as a
by-product. Moreover, this test determines the
structure of a phenol depending on the color that Hirano, J., Miyamoto, K., Ohta, H. (2008). The green
will be produced. When reacted with KMnO4, the and effective oxidation of alcohols to
solution with phenol produced a dark brown color carboxylic acids with molecular oxygen via
and precipitate settled at the bottom as a result of biocatalytic reaction. Tetrahedron
KMnO4 oxidizing the -OH group attached to the Letters, 49,1217-
aromatic ring. 1219.https://doi.org/10.10

References 16/j.tetlet.2007.12.032.

Ahluwalia, V. & Dhingra, S. (2004). Comprehensive McMurry, J. (2003). Fundamentals of Organic
Practical Organic Chemistry. India: Chemistry (5th ed.). USA: Thomson
Universities Press (India) Private
Limited 2000 McMurry, J. (2016). Organic Chemistry (9th ed.).
Boston: Cengage Learning.
Bettelheim, F.A. & Landesberg, J.M. (2013).
Laboratory Experiments for Introduction to
General, Organic, and Biochemistry (8th
ed.).
Solomons, G., Fryhle, C., & Snyder, S. (2014).
Organic Chemistry. US: John Wiley & Sons,
Inc.

Stoker, H. S. (2013). General, Organic, and
Biological Chemistry (6th ed.). US:
Brooks/Cole, Cengage Learning.