Experiment 7

Title: Properties of Alcohol

Name: Chong Zheng Yee ( P1 )

ID No.: 1404800
Subject: UDEC 1224 CHEMISTRY LABORATORY II
Name of Partner: Tan Herh Lim , Sia Ting Wai
Date: 7 JULY 2015
Lecturer: Dr. Mohammad Aminuzzaman

Objectives :
(i) To study the physical and chemical properties of alcohols.
(ii) To identify the two unknown liquids from their experimental observations.
(iii) To study the difference between primary alcohols, secondary alcohols and
tertiary alcohols.
Introduction :
Alcohols occur widely in nature and have many industrial and pharmaceutical
applications. In industry, alcohol is used both as a solvent and as a starting material for
production of carbonyl compound and carboxylic acid ( John E. McMurry, 2012).

Retrieved from : John E. McMurry (2012). Organic Chemistry, Eighth Edition, International
Edition, pp.628
Alcohols occupy a central position in organic chemistry. They can be prepared in
various ways such as hydration of alkene, hydroxylation of alkene, reduction of carbonyl
compound, reduction of carboxylic acid or ester, and Grignard reaction. However, another
method is used for the synthesis of methanol (CH3OH) , which is catalytic reduction of
carbon monoxide with hydrogen gas at 400 oC in presence of zinc oxide and chromia catalyst.
The reaction is shown below :
CO + 2H2 CH3OH

Alcohols are organic compounds that contain one or more hydroxyl (ROH)
functional group bonded to a carbon atom that is not bonded to a carbonyl carbon (C=O). If
the hydroxyl group is bonded to a benzene ring, it is classified as phenol, which will have
different properties compare to alcohols. At such, phenols is not suitable to be used in this
experiment. In addition, alcohols can be classified into three subclasses, which are primary
(1) alcohol, secondary (2) alcohol and tertiary (3) alcohol, depending on the number of alkyl
(R-) groups attached to the carbon atom with the hydroxyl (OH) group attached.

Retrived from :
http://chemwiki.ucdavis.edu/Organic_Chemistry/Organic_Chemistry_With_a_Biological_Em
phasis/Chapter_01%3A_Chapter_1%3A_Introduction_to_organic_structure_and_bonding_I
/Section_1.4%3A_Functional_groups_and_organic_nomenclature
Normally, alcohol are colourless liquid in room temperature. Their melting point and
boiling point are higher than similar size of alkane, alkene and alkyne due to its ablity to form
hydrogen bond with OH group. The oyxgen tend to pull the electron from the hydrogen,
enables the formation of temporary dipole-dipole interaction. Besides that, the ability to form
hydrogen bond also makes lower molar mass of alcohol soluble in water. As the OH group
of alcohol can form intermolecular hydrogen bond with water molecules. However, when the
length of the hydrocarbon chain of alcohol increased, the solubility of alcohol in water
decreased. This is because when the size of the hydrophobic hydrocarbon chain (non-polar
part) increases, the polarity of OH group will be cancelled out.
There are some chemical tests to distinguish between 1o, 2o and 3o alcohol. Which is
Lucas test, chromic acid test, and reaction with metallic sodium.
(i) Lucas Test
Lucas test is an experiment that was done in 1930 by Howard Lucas. After that, it is
utilized as a standard technique in organic chemistry experiments. However, this method is
not widely used in modern days as large number of spectroscopic and chromatographic

analytical methods have replaced it. 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 according to their reactivity. The reaction is a substitution reaction where the
chloride of the zinc chloride will be replaced by the hydroxyl group of the alcohol. The
reactivity of the alcohol with Lucas Reagent is measured by the degree of turbidity which
may vary from colorless to turbid (Madhulima Acharya, 2012). The positive result (formation
of turbid solution) happens due to the formation of chloroalkane, which is an insoluble solid.
Normally, tertiary alcohol will forms the precipitate faster than secondary alcohol, whereas a
primary alcohol does not form precipitate. The alcohol starting material must be sufficiently
soluble in aqueous environments of the Lucas reagent for the reaction to take place. Thus,
only water-soluble alcohols of low molecular weight would provide positive results in this
test
(ii) Chromic acid test
Chromic acid test is also known as Jones Oxidation. Historically, at 1943, the first
kinetic studies on chromic acid oxidation of isopropyl alcohol were performed by
Westheimer and Novick, the investigations had been carried out on the mechanism of
oxidation of hydrocarbons, aldehydes, ketones, carboxylic acids, ethers, olefins and glycols
as well as alcohols. After that, oxidation of a variety of organic compounds by chromic acid
has been extensively studied. Later in 1963, Bakore have studied the oxidation of a number
of hydroxyl acids and explained the mechanism on the basis of the Kwart-Francis scheme,
which is a minor variation of the well known Westheimer mechanism. (Mamta Mishra,
2014). Normally, chromic acid is prepared from chromium trioxide. Since chromic acid is a
strong oxidizing agent, it will oxidizes primary alcohol to carboxylic acid while orange Cr 6+
ions in chromic acid will be reduced to green Cr 3+ ions. On the other hand, secondary alcohols
will be oxidized to ketones, while tertiary alcohol will not be oxidized. (
http://www.chemhaven.org, 2015). The positive result is obtained if orange colour of mixture
turns to green colour.

(iii) Reaction with metallic sodium

Alcohols is a weak acids which will react with metallic sodium. The hydroxyl group
acts as a proton donor and release electron to form an alkoxide ion. Alkoxide ions will then
reacts with metallic sodium to form sodium alkoxide. The alkoxide ions that dissolved in an
alcohol is a strong base which same as hydroxide ion in water. This reaction will calibrate
hydrogen gas. The primary alcohol will have the fastest rate of calibration of hydrogen gas,
followed by secondary and tertiary alcohol.
In this experiment, the primary alcohol used is ethanol, secondary alcohol is isopropyl
alcohol while tertiary alcohol is t-butyl alcohol. Their structure is shown below:

Ethanol

Isopropyl alcohol

t-butyl alcohol

Chemicals :
ethanol (C2H5OH), isopropyl alcohol (C3H7OH), t-butyl alcohol (C4H9OH), Lucas reagent
(mixture of concentrated hydrochloric acid and zinc chloride), chromic acid, sodium metal
Glasswares :
Test tubes

Procedures :
(A) Solubility of Alcohols
1. In three separate dry test tubes, about 1 mL of each of the following: ethanol, isopropyl
alcohol and t-butyl alcohol was placed.
2. About 2 mL of water was added to each tube, mixed, and observed.
3. The results were recorded on the notebook.
4. The above procedures were repeated with the two unknown liquids, and observations were
made.
(B) Lucas test
1. To 1 mL portions of ethanol, isopropyl alcohol and t-butyl alcohol in separate dry test
tubes, 6 mL of Lucas reagent was added at room temperature.
2. The tubes were closed with a cork, shook, and the length of time it took for the mixture to
become cloudy or separate two layers was noted.
3. The results were recorded and the above procedures were repeated with the two unknown
liquids, and observations were made.
(C) Chromic acid test
1. To 2 mL portions of ethanol, isopropyl alcohol and t-butyl alcohol in separate dry test
tubes, 1mL of chromic acid solution was added.
2. Any changes in colour was observed.
3. The above procedures were repeated with the two unknown liquids, and observations were
made.
(D) Reaction with metallic sodium
1. To 2 mL portions of ethanol, isopropyl alcohol and t-butyl alcohol in separate dry test
tubes, a small piece of sodium metal was added and any reaction that occurs was noted.
2. The above procedures were repeated with the two unknown liquids, and observations were
made.

Results :
(A) Solubility of alcohols
Hydrocarbon
Ethanol

Observation
Soluble in water and form

Conclusion
Soluble in water

Isopropyl alcohol

colourless solution
Soluble in water and form

Soluble in water

t-butyl alcohol

colourless solution
Soluble in water and form

Soluble in water

Unknown A

colourless solution
Soluble in water and form

Soluble in water

Unknown B

colourless solution
Soluble in water and form

Soluble in water

colourless solution
(B) Lucas test
Hydrocarbon
Ethanol

Observation
The colourless solution
remains unchanged after

Isopropyl alcohol

t-butyl alcohol

Reaction equation

Unknown B

No reaction between
ethanol and Lucas

heating.
The solution turns cloudy

C3H7OH + HCl

reagent.
Reaction occurs after

after heating for 5

C3H7Cl + H2O

heating for 5 minutes.

minutes.
The colourless solution

C4H9OH + HCl

Reaction between t-

turns cloudy immediately

C4H9Cl + H2O

butyl alcohol and

without heating

Unknown A

Conclusion

Lucas reagent is

The solution turns cloudy

CxHyOH + HCl

occurs immediately.
Same reaction as

after heating for 5 minutes

CxHyCl + H2O

isopropyl alcohol so it

The colourless solution

CxHyOH + HCl

is a secondary alcohol.
Same reaction as t-

turns cloudy immediately

CxHyCl + H2O

butyl alcohol so it is a

without heating

tertiary alcohol.

(C) Chromic acid test

Hydrocarbon
Ethanol

Observation
The orange colour turns
dark green when chromic

Reaction equation
3 CH3CH2OH + 2

Conclusion
Ethanol is oxidized by
chromic acid.

acid is added.

CrO4- + 10 H+
3 CH3CHO + 2Cr3+ +
8 H2O

Isopropyl alcohol

The orange colour turns

(CH3)2CHOH + 2

Isopropyl alcohol is

dark green and precipitate

CrO4- + 14 H+

oxidized by chromic

formed after chromic acid

(CH3)2CO + 2Cr3+ +

acid.

is added.

t-butyl alcohol

8 H2O

The orange colour of

chromic acid remains

Unknown A

Unknown B

No reaction between t-

butyl alcohol and

unchanged.
The orange colour turns

R2CHOH + 2CrO4 +

chromic acid
Unknown A has the

dark green and precipitate

14 H+

similar reaction with

formed after chromic acid

R2CO + 2Cr3+ +

isopropyl alcohol and

is added.

8H2O

so it is secondary

The orange colour of

chromic acid remains

unchanged.

alcohol.
Unknown B has the
similar reaction with tbutyl alcohol and so it
is tertiary alcohol.

(D) Reaction with sodium metal

Hydrocarbon
Ethanol

Observation
The reaction is fast.

Reaction equation
2C2H5OH + 2Na

Conclusion
Large amount of

Bubbles of colourless gas

2C2H5ONa + H2

are produced.

hydrogen gas is
released from the
reaction between
ethanol and sodium.

Isopropyl alcohol

The reaction is moderate.

2C3H7OH + 2Na

Rate of reaction is fast

Moderate amount of

Bubbles of colourless gas

2C3H7ONa + H2

hydrogen gas is

are produced.

released from the

reaction between
isopropyl alcohol and
sodium. Rate of

t-butyl alcohol

The reaction is slow.

2C4H9OH + 2Na

reaction is moderate.
Less hydrogen gas is

Bubbles of colourless gas

2C4H9ONa + H2

released from the

are produced

reaction between tbutyl alcohol and

sodium. Rate of

Unknown A

The reaction is moderate.

2CxHyOH + 2Na

reaction is slow.
Unknown A has the

Bubbles of colourless gas

2CxHyONa + H2

similar reaction as

are produced

isopropyl alcohol and

so it is secondary

Unknown B

The reaction is slow.

2CxHyOH + 2Na

alcohol.
Unknown B has the

Bubbles of colourless gas

2CxHyONa + H2

similar reaction as t-

are produced

butyl alcohol and so it

is tertiary alcohol.

Discussion :
For part A, ethanol, isopropyl alcohol and t-butyl alcohol are soluble in water because
they contain OH group which would form a hydrogen bond with the water molecule.
Moreover, there are short hydrocarbon-chain alcohol. The solubility of alcohol depends on
the size of the hydrocarbon chain of alcohol. The larger the size of the hydrocarbon-chain of
alcohol, the lower the solubility of the alcohol. In order for an long hydrocarbon-chain

alcohol to dissolve in water, intermolecular hydrogen bonding between water molecules will
first be broken down to make a large space for the long hydrocarbon chain alcohols.
However, only the OH- group of the alcohol are able to form back the intermolecular
hydrogen bonding with water, while the hydrocarbon chain of alcohols will not form
hydrogen bonding with water molecules. Hence, a lot of original hydrogen bondings that
were broken earlier did not replaced by new ones. Instead, Van der Waals forces between the
hydrocarbon chain and the water molecules would replace the hydrogen bonding. As a result,
not enough hydrogen bonds are reformed to compensate back the energy for the hydrogen
bonds that had been broken earlier. When this disruption became large enough, the water
molecules would repelled the alcohol molecules effectively to reform the hydrogen bonding.
Thus, the alcohol will not soluble in water. This explained why the solubility of alcohols
decreased when size of the hydrocarbon chain of alcohols increase. (Chemguide.co.uk, 2015).
Based on the table below, the alcohols which contains more than 8 carbons are insoluble in
water.

Retrieved from :
http://chemed.chem.purdue.edu/genchem/topicreview/bp/2organic/alcohols.html
t-butyl alcohol still can dissolved easily in water because it has branched alkyl group.
This feature reduces the surface area of the hydrophobic part and making it soluble in water.
Next, ethanol and isopropyl alcohol are soluble in water because the size of their hydrocarbon
chain is small enough. Both unknown A and B were soluble in water, which means that they

are alcohol which consists of 8 or less carbon atom. The experimental result are shown
below:

The experimental results for part A are shown below:.

Ethanol

Isopropyl t-butyl
alcohol

alcoho
l

Unknown A

Unknown B

For part B, when colourless t-butyl alcohol is added with Lucas reagent, an instant reaction
occur and positive result was obtained where turbinity formed and the solution turns cloudy
due to the formation of chloroalkane, which is an insoluble solid. Next,when isopropyl
alcohol added with Lucas reagent, the solution remains unchanged before heating but after 5
minutes of heating, positive result was obtained where turbinity was formed which turns the
solution cloudy .This means that the reaction between secondary alcohol and Lucas reagent is
slower than tertiary alcohol as it required heat. Furthermore, when ethanol is added with
Lucas reagent, the colourless solution remains the same before and after 5 minutes of heating.
This is because primary alcohol do not react with Lucas reagent. Apart from that, unknown A
had similar observation as isopropyl alcohol, whereas unknown B had similar observation as tbutyl alcohol.
The experimental result for part B (before heating) are shown below :

Ethanol

Isopropyl

t-butyl

alcohol

alcoho

Unknown A

Unknown B

l
The experimental result for part B (after heating) are shown below :

Ethanol

Isopropyl

t-butyl

Unknown A

Unknown B

negative

alcohol

alcohol

positive test

positive test

test

positive

positive

test

test

Lucas reagent is basically a solution which is formed by the combination of HCl and ZnCl2.
In this case, zinc chloride acts as catalyst. Normally, alcohol and Lucas reagent reacts as follows :

Retrieved from :
http://academics.wellesley.edu/Chemistry/chem211lab/Orgo_Lab_Manual/Appendix/Classifi
cationTests/alcohol.html
The chemical reactions for ethanol, isopropyl alcohol, and t-butyl alcohol with Lucas
reagent is as follows :

Ethanol

Isoprop
yl
alcohol

t-butyl
alcohol

The general mechanism for this reaction is :

Retrieved from : http://organicchem.org/oc2web/lab/exp/oxid/lucas.pdf

Reaction for Lucas test is a SN1 nucleophilic substitution. In the first step, the proton
(H+) from Hydrochloric acid (HCl) will protonate the OH-group of the alcohol, forming the
oxonium ions, which is unstable. Then OH2+ accept an electron and leave the group to form
water molecule. In next step, carbocation formed would react with Cl- to form the alkyl
product. The reactivity of alcohols in Lucas test is determined by the stabilities of the
carbocation intermediates.
The carbocation stability of alcohols are arranged in decreasing order as follows:

Higher stability of carbocation which have higher reactivity toward Lucas reagent.
Since tertiary carbocation is more stable, they will undergo reaction and form turbid solution
faster compare to secondary carbocation. Primary alcohol do not react with Lucas reagent
because primary carbocation is the unstable. Thus, the classes of alcohol for unknown A and
unknown B could be determine with this information. Unknown A which require heating to
form alkyl chloride is a secondary alcohol, while unknown B which form alkyl chloride
immediately is a tertiary alcohol.

For part C, when t-butyl alcohol was treated with chromic acid, the solution turns
from colourless to orange due to presence of Cr6+ ions, which shows a negative result. Next,
when isopropyl alcohol was added with chromic acid, two layers solution formed with
greenish solution on top and dark colour on bottom, indicating a positive result. Moreover,
when ethanol was added with chromic acid, the solution turned from colourless colour to a
black layer. The black layer is actually the dark green colour, it is hard to differentiate
because the light is not enough in the laboratory. Thus, it is actually showing a positive result.
Apart from that, unknown A shows the positive result with green colour solution formed in
chromic test, while unknown B shows negative result.
In the reaction between alcohol and chromic acid, a positive result will gives a green
colour change because the orange colour of Cr6+ ions in mixture are reduced to green colour
Cr3+ ions. Chromic acid is a strong oxidzing agent which oxidizes primary alcohol to
aldehyde and then the aldehyde will continue oxidized by chromic acid to carboxylic acid.
Secondary alcohol will oxidized by chromic acid to ketone while tertiary alcohol will not
oxidized by chromic acid.

The experimental result for part C are shown below :

Ethanol

Isopropyl t-butyl

Unknown

Unknown B

positive

alcohol

alcohol

negative test

test

positive

negativ

positive

test

e test

test

However, chromic test can only differentiate a tertiary alcohol with primary or
secondary alcohol because both primary and secondary alcohol can be oxidised by Cr6+ ions.
Hence, from this test, we can identify unknown B as tertiary alcohol whereas unknown A is
primary or secondary alcohol.
The reaction of primary alcohol with chromic acid is shown below :

The reaction of secondary alcohol with chromic acid is shown below :

Retrieved from : http://www.harpercollege.edu/tmps/chm/100/dgodambe/thedisk/qual/chromic.htm

The chemical reaction between ethanol and chromic acid :

Retrieved from : http://science.uvu.edu/ochem/index.php/alphabetical/c-d/chromic-acid/

The mechanism of formation of chromic acid is shown below :

Retrived from : http://www.name-reaction.com/jones-oxidation

The mechanism of reaction between secondary alchohol and chromic acid is shown below:

Retrieved from : http://www.name-reaction.com/jones-oxidation

For part D, all types of alcohol used in this experiment will reacts with metallic
sodium to produce hydrogen gas due to the presence of OH- group.
Ethanol

isopropyl alcohol

Unknown A

t-butyl alcohol

Unknown B

For ethanol : 2C2H5OH + 2Na 2C2H5ONa + H2

For isopropyl alcohol : 2C3H7OH + 2Na 2C3H7ONa + H2
For t-butyl alcohol : 2C4H9OH + 2Na 2C4H9ONa + H2
However, the rate of evolution of hyrogen gas is different. This is due to the different
acidity of alcohol. The more acidity the acid, the faster the evolution of hydrogen gas. In this
experiment, the evolution of hydrogen gas is fastest in ethanol, followed by isopropyl
alcohol, and finally t-butyl alcohol. Thus the acidity of the alcohols decreasing in this way:
Ethanol > isopropyl alcohol > t-butyl alcohol
When comparing unknown A and unknown B, the rate of evolution of hydrogen gas is
higher for unknown A. Thus, A is more acidic than B.
There are 2 factor affecting the acidity of alcohol, which are steric effect and
inductive effect. For steric effect, the bulky group will block the water molecules from

approaching the alkoxide ions to solvate the alkoxide ions. Hence, for the bulky alcohol, the
formation of alkoxide ions will became energetically unfavored and decrease the acidity of
alcohol. On the other hand, the second factor is inductive effect, the alkyl group is a electron
donating group, the more bulky the alkyl group, the stronger the electron donor effect. Hence,
when the size of alkyl group is big, a stronger inductive effect will be produced. This will
destabilize the alkoxide ion and decrease the acidity of alcohol.

Conclusion :
Ethanol, isopropyl alcohol and t-butyl alcohol are soluble in water. For Lucas test, secondary
alcohol and tertiary alcohol shows reaction towards Lucas reagent except primary alcohol.
The tertiary alcohol show fastest reaction with Lucas reagent. For chromic acid test, primary
alcohol and secondary alcohol react with chromic acid except tertiary alcohol. Lastly, for
reaction with sodium metal, primary alcohol is more reactive toward sodium metal while
tertiary alcohol has the lowest reactivity toward sodium metal.All the reactions of unknown A
are same with that of isopropyl alcohol, therefore unknown A is secondary alcohol. For the
unknown B, the all reaction is same with the t-butyl alcohol. Therefore, the unknown B is
tertiary alcohol.

Reference :
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