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ALCOHOLS AND PHENOLS

Abstract

The experiment was aimed to differentiate the three types of alcohols and distinguish the
reactions of alcohols and phenols. Qualitative tests were done such as solubility of alcohols and
phenols; reaction of alcohols with sodium metal, potassium dichromate, hypohalite, Lucas test
and reaction of phenols with ferric chloride. According to the results, it was shown that alcohols
with below 8 carbon chain and less compact alcohol compound were soluble in water, also, it
was shown that saturated alcohols were soluble in concentrated H 3PO3 while unsaturated were
insoluble. In solubility of phenols, it was found to be that phenols with to benzene ring or greater
molecular weight were insoluble with water such as 2-naphtol while p-chlorophenol, resorcinol
and salicylic acid were soluble in water. In test of sodium metal, it was found out that all types of
alcohols would show exothermic reaction upon addition of sodium metal. In determining the
type of alcohols Lucas reagent was used and based on the results, tertiary alcohol would react
first followed by a secondary alcohol and so forth. In test with oxidizing agent such potassium
dichromate, primary alcohol was found to be easily oxidized to aldehyde and over oxidized to
form carboxylic acid, likewise, the secondary alcohol was able oxidized to form a ketone
compound while the tertiary did not undergo oxidation due to its lack H atom to react with the
reagent. The addition of Iodine in NaOH solution in the Iodoform test also detected the presence
of a methyl ketone in isopropyl alcohol and reacted with ethanol to form a yellow precipitate
which was called iodoform. In ferric chloride test, the p-chlorophenol, 2-naphtol, resorcinol,
salicylic acid shown positive reaction which exhibited different characteristics of colors upon
addition of ferric chloride. The experiment was done due to help the author being a chemistry
major student fully discern the characteristics and types of the alcohol and phenols.
Introduction

Alcohols and phenols can be thought of as organic derivatives of water in which one of
the water’s hydrogens is replaced by an organic group: H - O - H versus R - O - H and Ar - O -
H. In practice, the group name alcohol is restricted to compounds that have their -OH group
bonded to a saturated, sp3-hybridized carbon atom. Alcohols are classified as primary (1°),
secondary (2°), or tertiary (3°), depending on the number of organic groups bonded to the
hydroxyl-bearing carbon (McMurry, 2016). Representative examples of a phenol, and three types
of alcohols are shown below.

Figure 1. Types of Alcohols

These four classes of compounds contain the functional group OH, the unique differences
in their reaction chemistry allows one to easily differentiate one from the other. The solubility of
alcohol is determined by the hydroxyl group present. The hydroxyl group in alcohol is involved
in the formation of intermolecular hydrogen bonding. Thus, hydrogen bonds are formed between
water and alcohol molecule which makes alcohol soluble in water. However, the alkyl group
attached to the hydroxyl group is hydrophobic in nature. Hence, the solubility of alcohol
decreases as the size of alkyl group increases (Robert and Caserio, 1977).  Lucas reagent is made
up of zinc chloride in concentrated hydrochloric acid. Testing using this reagent depends on the
different rate of conversion of primary, secondary and tertiary alcohol to their chloride forms.

Phenols are more characterized by a hydroxyl group attached to a carbon atom that is part
of an aromatic ring. Phenols are more soluble than alcohol since it can form stronger hydrogen
bonds and more acidic than alcohols (Robert and Caserio, 1977). The hydroxyl group of a phenol
compound attached to unsaturated carbon atoms will react with ferric chloride to give red,
purple, coloration depending on the phenol’s structures.
The experiment was done due to help the author being a chemistry major student fully
discern the characteristics and types of the alcohol and phenols. Furthermore, the experiment was
conducted to differentiate the three types of alcohols and distinguish the reactions of alcohols
and phenols.

Experimental (Methods and Materials)

In the course of the experiment, the instructor explained the theoretical reactions of the
different types of alcohol and phenols which can be found on the laboratory manual “Chemistry
127.2- Organic Chemistry I- Lab” (Villar, 2019). The materials used in the experiment were 10
mL n-butyl alcohol, 10 mL sec-butyl alcohol, 10 mL Ethyl alcohol, I2 in KI solution, 10 mL
isopropyl alcohol, 10 ml tert-butyl alcohol, cyclohexanol, 3% FeCl3 solution, 5% K2Cr3O7, 2-
naphthol, 100 mL Lucas reagent, 2M H2SO4, catechol, 10 % NaOH, Resorcinol, 15 M Test
tubes, 10 Med droppers, Test tube rack, water bath, screen for test tubes, hot plate and wash
bottle. The experiment was divided into two: the properties and reactions of alcohols and lastly,
the properties and reactions of phenols.

Part 1. Properties and Reactions of Alcohols


A. Solubility in water and in acidic solution
10 mL of n-butyl alcohol, tert-butyl alcohol, cyclohexanol and benzyl alcohol was
placed into four separate test tubes. Then, 5 mL of distilled water was added to each
sample. It was mixed thoroughly and observed the reactions. Afterwards, the test tube
was placed in a water bath and warmed at 65 oC. A drop of each solution was taken and
test on the blue litmus paper. The samples were then removed from the water bath and
was cooled down in a room temperature. The steps were repeated using equivalent
volumes of phosphoric acid, instead of water. The test tube was shaken to mix each
solution but it shouldn’t be heated.
B. Reaction with sodium metal
10 drops of ethyl alcohol, isopropyl alcohol, and tert-butyl alcohol were placed in
a separate dry test tube. Each test tube was added with a small a piece of sodium metal,
then, the reaction was observed as it proceeds to completion. Lastly, all observations
were recorded.
C. Reaction of Alcohol with Lucas Reagent
5 drops of Lucas reagent was placed into three dry test tubes. Afterwards, 3 drops
of ethyl alcohol, isopropyl alcohol and tert-butyl alcohol were placed into each test tube.
Then, the test tube was placed in a hot bath for few minutes, if there were no cloudiness
observed. The length of time it takes for the mixture to became cloudy or to separate into
two layers was recorded.
D. Reaction with Potassium dichromate
5 drops of ethyl alcohol, isopropyl alcohol and tert-butyl alcohol were placed into
separate test tubes. Then, 10 drops of potassium dichromate in dilute sulfuric acid was
added to each test tubes. The test tubes were shaken and placed in a warm water bath.
Then, the changes were observed. The flask containing ethyl alcohol and isopropyl
alcohol sample were removed and placed into boiling water bath. Afterwards, the
mixtures were brought to boil and the moistened blue litmus paper was placed over the
mouth of each test tube using a tweezer. After 10 minutes, each test tube was inspected
and observation was recorded.
E. Reaction with hypohalite
5 drops of ethyl alcohol, isopropyl alcohol and tert-butyl alcohol were placed into
separated test tubes. Then, 10 drops of distilled water were added and 5 drops I2 / KI
solution was added. While, shaking the test tube 10% NaOH was added until the iodine
color (reddish orange) disappeared and the solution turned to faint yellow. The content of
the test tube was examined and the odor was noted. Afterwards, if the test tube had no
changes observed, it was then shaken and heated in water bath for 2 minutes. The mixture
was again examined and observations were recorded.

Part 2. Properties and Reaction of Phenols


A. Solubility in water
5 drops of p-chlorophenol, 2-napthol, resorcinol and salicylic acid were placed
into different separate test tube. 5 mL of distilled water was then added into each test tube
and was mixed and observed. The test tube was placed in a water bath at 65 oC , then, a
drop of each solution was taken and tested using blue litmus paper. Afterwards, the test
tubes were removed from the water bath and cooled down to room temperature. Finally,
the observation was recorded.
B. Ferric Chloride Test
20 drops of 95% ethanol were placed into four separate test tubes. Then, 2 drops
of p-chlorophenol, 2-napthol, resorcinol and salicylic acid were added to each of the test
tube. Afterwards, 2 drops of 1% FeCl3 solution was added and mixed thoroughly. Finally,
the observation was recorded.
C. Bromine Water test
Bromine water was added dropwise until the reddish orange color of bromine is no longer
discharged using the samples in Part A. After the addition, it was shaken well. The
number of drops consumed was noted.

Results and Discussion


Part 1. Properties and Reaction of Alcohols
Table 1. Solubility of Alcohols in Water and in Acidic Solution
Samples In Water Acidity In Phosphoric Acid
n-butyl alcohol Soluble Acidic Soluble
Tert-butyl alcohol Soluble Acidic Soluble
Cyclohexanol Soluble Acidic Soluble
Benzyl alcohol Insoluble Acidic Insoluble

Table 2. Reaction of Alcohols with Sodium Metal


Samples Reaction Description
Ethyl alcohol Exothermic; Most reactive; formation of gas
Isopropyl alcohol Exothermic; Moderate reactive; formation of gas
Tert-butyl alcohol Exothermic; Lest reactive; formation of gas

Table 3. Reaction of Alcohol with Lucas Reagent


Samples In room temperature In hot water bath
Ethyl alcohol No cloudy formation No cloudy formation
Isopropyl alcohol No cloudy formation Cloudy formation (7 mins)
Tert-butyl alcohol Cloudy formation (3 mins) Cloudy formation

Table 4. The Reaction of Alcohols with Potassium dichromate


Samples After Steam Bath After Hot Bath Acidity
Color of the solution Color of the solution Acidic
Ethanol turned brownish to turned green
dark brown
Isopropyl alcohol Color of the solution Color of the solution Acidic
turned brownish to turned dark green
dark brown
Tert-butyl alcohol Color of the solution No reaction Acidic
turned light orange to
dark orange

Table 5. The Iodoform Reaction


Samples Reaction at room temp. Reaction after water bath
Ethyl alcohol No reaction Faint yellow color
Tert-butyl alcohol No reaction No reaction
Isopropyl alcohol Formation of a yellow precipitate Not performed

Part 2: Properties and Reactions of Phenols

Table 6. Solubility of in Water


Sample In water In water bath pH Observation at room temp.
at 65 oC
p-chlorophenol Soluble Soluble 3 to 5 Cloudy and separation of liquid
2-napthol Insoluble Insoluble 3 to 5 2 layers (crystal formation above
while insoluble below)
Resorcinol Soluble Soluble 2 to 5 No changes
Salicylic acid Insoluble Soluble 1 to 5 Formation of crystals

Table 7. Ferric Chloride Test


Sample Color Observation
p-chlorophenol Azul blue
Resorcinol Black
Salicylic acid Violet
2-naphthol Army green to yellow

C. Bromine Water Test


Reaction Description
p-chlorophenol
2-naphthol
Resorcinol
Salicylic acid
*not performed
Based on the result in table 2, the three alcohols: ethyl alcohol, isopropyl alcohol and tert-
butyl alcohol reacted with sodium metal. It is because alcohols react with sodium to form a salt
(sodium alkoxide) and hydrogen gas. The reaction was similar but much slower than the reaction
of water and sodium. It is due to the similarities in the structure of the water molecule and the
alkyl (-OH) group in alcohols. Due to the low density of the alcohols the sodium sinks. The
reaction proceeds steadily with the evolution of hydrogen gas and leaves a colorless solution of
the salt. The salt can be recovered as a white solid by careful evaporation of the solution (Clerk,
2003). Furthermore, the primary alcohol was the most reactive since it closest to that of the
structure of water and trend decreases as the alcohol become more substituted. Hence, the
experiment was successful since it is inline with the theoretical. All are exothermic reactions
with the chemical formula:
2R-OH + 2Na 2RO-Na+ + H2

The Lucas reagent is a solution of anhydrous zinc chloride (Lewis acid) in concentrated


hydrochloric acid. It is used as a reagent to test alcohols and classify them in accordance to their
reactivity. The reaction is a substitution reaction where the chloride of the zinc chloride gets
replaced by the hydroxyl group of the alcohol. The stability of the alcohol which determines the
rate of the reaction. The alkyl halide formed is insoluble, and its formation causes the solution to
become turbid (Kjonaas and Riedford, 1991). Based on the results, the tert-butyl alcohol was the
first to react with the Lucas reagent, since tert-butyl alcohol is a tertiary alcohol (which gives 3
degree carbocation) which give very stable carbocations on losing water after protonation and
readily reacts with the reagent. Hence, it reacts faster among the two alcohols and gives
immediate turbidity. On the other hand, the secondary and primary alcohols did not react with
the reagent at room temperature, thus, it was subjected to the hot water bath. The only alcohol
that shown turbidity at 7 minutes was the isopropyl alcohol which is a secondary alcohol, since
secondary alcohol reacts slower as their carbocation (2 degree) are not as stable as like tertiary
alcohol. While, primary alcohol like ethanol did not react at all, since it is due to the carbocation
of the primary alcohol was unstable. Turbidity appearing in the reaction mixture is taken as
evidence of a positive reaction following the equations shown below:
Potassium dichromate is commonly identified as oxidizing agent. Oxidation of alcohols
was basically removing H atom to react with the oxygen in the oxidizing reagent. Primary
alcohol when oxidized produces aldehyde and further oxidized to produce carboxylic acid.
Secondary alcohols can also be oxidized producing a ketone. On the other hand, tertiary alcohol
did not undergone oxidation due to lack of free hydrogen atoms (Clark, 2003). This explains why
the ethyl alcohol and isopropyl alcohol only exhibited color change after water bath, since they
were primary and secondary alcohols respectively. While, tert-butyl alcohol was consistent at
orange color which exhibited no change after water bath. The green color was observed which
indicate positive reaction of the presence of primary and secondary alcohols. Blue litmus paper
was used to determine the acidity of the solution, it turned out that the remaining water from the
alcohol lea to acidic solution. The following chemical reaction are shown below:

Iodoform test was used to test the presence of alcohols with the structure RCH(OH)CH 3.
A solution of I2 was added to small amount of an alcohol followed by NaOH to remove the color
of the iodine. Iodoform was distinctively identified as the yellow precipitate and had a faintly
medical smell. Based on the results, isopropyl alcohol and ethanol was the only to form a yellow
precipitate of iodoform, CHI3. Since, When the alcohol is combined with sodium hydroxide
(NaOH) and Iodine, the resulting sodium hypoiodite (NaOI) will cause the oxidation like the
primary and a secondary alcohol which are shown below. Then, the intermediate ketone and
aldehyde is further oxidized to give a carboxylic and iodoform (Clark, 2014).

CH3CHOH + NaOI CH3C(=O)H + NaI + H2O


CH3CH(OH)CH3 + NaOI CH3C(=O)CH3 + NaI + H2O
R-C(=O)CH3 + 3NaOI RC(=O)Cl3 + 3NaOH
R-C(=O)Cl3 + NaOH RC(=O)O- Na+ + CHI3

On the other hand, tert-butyl alcohol did not react at all since it is a tertiary alcohol and it
does not have available hydrogen to give up. Hence, no intermediate ketone was formed.

In table 6, it shown that only p-chlorophenol and resorcinol were soluble in room
temperature. Since, they are polar compounds and has a hydroxy group which would form
hydrogen bonding with water. Furthermore, it due to it weak acidic nature which make soluble
with water. On the other hand, salicylic acid and 2-napthol were insoluble since salicylic acid
contains 7 carbon atoms in its molecule, 6 of which are in a carbon ring along with hydrogen and
oxygen. Its substance is more closely related to oil that resists bonding with water, however its
solubility is influenced by temperature (Shalmashi and Eliassi, 2008). Hence, when the salicylic
acid was subjected to water bath it became soluble. The 2-napthol was insoluble due its
molecular weight, as the size of the chain increase the solubility decreases.
In ferric chloride test, all samples shown different characteristic of colors. For the reason
that compounds with a phenol group will form a complex ion which causes the color blue, violet,
purple, green, or red-brown color upon addition of aqueous ferric chloride (Clark, 2004).

Conclusion

Based on the result of the experiment, the students were able to differentiate the three
types of alcohols through Lucas test and understand the reactions of alcohols such as primary
alcohol can undergo oxidation to produced aldehyde and carboxylic acid while secondary
alcohol can oxidize to produced ketone. Furthermore, the students were able to distinguish the
reaction of phenols like when treated with ferric chloride, it produces complex ion that exhibit
intense colors.

Reference

John D. Robert and Marjorie C. Caserio (1977) Basic Principles of Organic Chemistry, second


edition. W. A. Benjamin, Inc. , Menlo Park, CA. ISBN 0-8053-8329-8. 

McMurry, J. (2016). Organic Chemistry.9th Edition. Cengage Learning. pp. 525-526

Festin, A.J. and Raquepo, V.V. (2014). Solubility Classification Using Water, 5% NaOH, 5%
HCl, 5% NaHCO3 , Ether, Concentrated H2SO4 and 85% H3PO4 . Retrieved from,
https://www.academia.edu/6416813/Solubility_Classification_Using_Water_5_NaOH_5_HCL_
5_NAHCO3_Ether_Concentrated_H2SO4_and_85_H3PO4.

Clark, J. (2003). REACTING ALCOHOLS WITH SODIUM. Retrieved from,


https://www.chemguide.co.uk/organicprops/alcohols/sodium.html.

Clark, J. (2004). THE TRIIODOMETHANE (IODOFORM) REACTION WITH ALCOHOLS.


Retrieved from, https://www.chemguide.co.uk/organicprops/alcohols/iodoform.html

Kjonaas, R. A and Riedford, B. A. (1991). "A Study of the Lucas Test". Journal of Chemical
Education. 68 (8): 704. 

Shalmashi, A. and Eliassi, A. (2008). Solubility of Salicylic Acid in Water, Ethanol, Carbon
Tetrachloride, Ethyl Acetate, and Xylene. Journal of Chemical & Engineering Data. 53 (1): 199-
200 DOI: 10.1021/je7004962