EXPERIMENT 4

PROPERTIES OF ALCOHOL
Objective:
To study the physical and chemical properties of alcohol.
To identify the differences between primary alcohol, secondary alcohol and tertiary alcohol.
Introduction:
Alcohols are compounds in which one or more hydrogen atoms in an alkane have been
replaced by an –OH group. For example:
CH 3-OH CH 3−CH 2-OH CH 3−CH 2−CH 2-OH

Methanol Ethanol 1-Propanol

Alcohols fall into different classes depends on how the –OH group is positioned on the chain
of carbon atom. Here are some examples of differences between the various type.
Primary alcohols:
In a primary (1˚) alcohol, the carbon that carries the –OH group is only attached to one alkyl
group. Example is Ethanol.
Secondary alcohol:
In a secondary (2˚) alcohol, the carbon with the –OH group attached is joined to two alkyl
groups, which may be the same or different. Example is Propan-2-ol.
Tertiary alcohol:
In a tertiary (3˚) alcohol, the carbon holding the –OH group is attached to three alkyl groups,
which may be any combination of same or different. Example is 2-methylbutan-2-ol.
Physical properties
The larger the alcohol, the higher the boiling point. Small alcohols are water soluble because
the hydroxyl groups can hydrogen bond with water molecules. As the size alkyl group
increases, the solubility in water decreases. This is the result of alkyl group disrupting
hydrogen bonding among the water molecules. If the disruption become large enough the
water molecules, in effect, expel the alcohol molecules to re-established hydrogen bonding.
Chemical Properties
1. Lucas Test
This test able to differentiate between primary, secondary and tertiary water soluble
alcohols. Lucas reagent is a mixture of concentrated hydrochloric acid and zinc
chloride. Zinc chloride is Lewis acid, which when added to hydrochloric acid makes it
more acidic. Tertiary alcohols react with Lucas reagent almost immediately to form
an alkyl chloride which is insoluble. The formation of a second liquid phase in the test
tube almost as soon as the alcohol initially dissolves is indicative of a tertiary alcohol.
 A secondary alcohol reacts slowly to form a chloride and, after heating a little, gives a
second phase, usually within 10 minutes. Primary alcohols and methanol do not react
under these conditions.

2. Chromic Acid Test

In this test, primary alcohols are oxidised to carboxylic acids by chromic acid. The
+6 +3
Cr in the chromic acid, which is red-brown is reduced to Cr , which is green.
Secondary alcohols are oxidised to ketones by chromic acid. The chromium reduction
is the same here as for the primary alcohols. Tertiary alcohols are not oxidised by
chromic acid. Thus, this reaction can differentiate between primary, secondary and
tertiary alcohols.

3. Reaction with Metallic sodium

Alcohols like water, are weak acids. The hydroxyl group can act as a proton donor to
form an alkoxide ion. Alkoxide ions dissolved in alcohol, like hydroxide ions in
water, are strong bases which can be prepared by the reaction of an alcohol with
sodium metal. This reaction produces hydrogen gas(an introduction to alcohols, 2015).
+ ¿+ H2 ¿

2 R−OH +2 Na → 2 R−O−¿ Na ¿

An alkoxide
Materials and apparatus:
Ethanol (C 2 H 5 OH ¿, isopropyl alcohol (C 3 H 7 OH ¿, t-butylalcohol (C 4 H 9 OH ¿, Lucas
reagent, Chromic acid and Sodium metal.
Test tubes
Experimental procedure:
A) Solubility of alcohols
 1mL of ethanol, isopropyl alcohol and t-butyl alcohol was poured into 3
separate dry test tubes.
 2mL of water was added to each test tube and mixed.
 The changes were observed and results were recorded.
 The above process was repeated with two unknown liquids.
B) Lucas Test
 1mL of ethanol, isopropyl alcohol and t-butyl alcohol was poured into 3
separate dry test tubes.
 6mL of Lucas reagent was added to the test tubes at room temperature.
 Tubes were closed with cork and shook.
 Time taken for the mixture to turn cloudy or separate into 2 layers were
noted.
 Results was recorded.
 The above process was repeated with two unknown liquids.
C) Chromic acid Test
 2mL of ethanol, isopropyl alcohol and t-butyl alcohol was poured into 3
separate dry test tubes.
  1mL of chromic acid was added to the test tube.
 Changes in colour was observed.
 The above process was repeated with 2 unknown liquids.
D) Reaction with metallic sodium
 2mL of ethanol, isopropyl alcohol and t-butyl alcohol was poured into 3
separate dry test tubes.
 A small piece of sodium metal was added.
 Changes in reaction, gas formed was observed.
 The above process was repeated with 2 unknown liquids.
Results:
A) Solubility of alcohols
Hydrocarbons Observation
Ethanol Soluble in water
Isopropyl alcohol Soluble in water
t-Butyl alcohol Soluble in water
Unknown A Soluble in water
Unknown B Soluble in water

B) Lucas Test
Hydrocarbon Observation
Ethanol Solution remain unchanged
Isopropyl alcohol Solution remain unchanged
t-Butyl alcohol Solution form 2 layers with clear upper
layer and cloudy lower layer
Unknown A Solution remain unchanged
Unknown B Solution form 2 layers with clear upper
layer and cloudy lower layer

C) Chromic acid Test

Hydrocarbon Observation
Ethanol Solution turns dark green
Isopropyl alcohol Solution form 2 layers with green upper
layer and black lower layer
t-Butyl alcohol Solution turns to reddish brown
Unknown A Solution form 2 layers with green upper
layer and black lower layer
Unknown B No reaction

D) Reaction with metallic sodium

Hydrocarbon Observation
Ethanol Colourless bubbles release vigorously
Isopropyl alcohol Colourless bubbles release slowly
t-Butyl alcohol Colourless bubbles release slower
 Unknown A Colourless bubbles release slowly
Unknown B Colourless bubbles release very slow

Discussion:
Ethanol, isopropyl alcohol, t-Butyl alcohol are short alkyl chain alcohols. Alcohols soluble in
water because of the presence of hydroxyl group (–OH) in the compound. The hydroxyl
group can form hydrogen bond with water molecules and make it soluble in water.
Solubility of alcohols in water depends on its size and structure. When the size of alcohol
increase, the solubility of alcohol will decrease. Usually, when the number of carbon per
molecule is more than 6 it will not dissolve in water. Based on the solubility of alcohol in
water, the information above is not enough to clearly distinguish between the alcohols as all
the alcohols are soluble in water.
In order to distinguish between the alcohols, the second test called Lucas test is conducted.
Lucas test is used to differentiate between primary alcohols, secondary alcohols and tertiary
alcohols as well. Normally for Lucas test, formation of 2 layers is said to be a positive test.
The 2 layers are aqueous layer and cloudy layer. The second layer formed in the solution
which is cloudy layer is insoluble because it is alkyl chloride. The alkyl chloride produced
from the above reaction is not soluble in water and cause cloudiness to form in the aqueous
solution.
When Ethanol was added with Lucas reagent, the yellowish solution remain unchanged. This
is because, ethanol is a primary alcohol so it do not react with Lucas reagent. The same goes
to isopropyl alcohol and Unknown A which remain unchanged too. This indicate the reaction
between Lucas reagent and secondary alcohols is slow. Whereas, the solution in t-butyl
alcohol and Unknown B formed 2 layers with upper clear upper layer and cloudy lower layer.
This indicate the reaction between Lucas reagent and tertiary alcohols is this shows that SN 1
Nucleophilic substitution take place in Lucas test. Alcohols with the properties of generating
a stable carbocation intermediates will undergo this Nucleophilic substitution. The –OH
group in alcohol attracts the hydrogen in hydrochloric acid to form oxonium ion and leave the
−¿¿
group to form water. The carbocation intermediate is formed and react with Cl to produce
an alkyl halide product

|
(nucleophilic substitution images - Bing images, 2019)

The aim of Chromic acid test in this experiment is to differentiate the primary and secondary
alcohol. In the reaction between alcohol and chromic acid, the chromic acid which is
Chromium (IV) ions, Cr 6+¿ ¿ is reduced to Chromium (III) ion, Cr 3+¿ ¿. The green colour
represent the positive test for Chromic acid. Test tube with ethanol, isopropyl alcohol and
Unknown A, the solution turns to from colourless to green. This reaction happened due to the
Chromium (IV) ions, Cr 6+¿ ¿are reduced. For isopropyl alcohol, the layers were formed with
green upper layer and black lower layer. This indicate that the isopropyl alcohol reacted with
chromic acid due to the secondary alcohol is readily oxidised. The black layer formed in
isopropyl alcohol is actually dark blue colour which cannot be seen clearly in the experiment.
The t-butyl alcohol changed from the colourless solution to reddish brown
precipitate(Functional Groups - The Chromic Acid Test, 2019). This indicate t-butyl alcohol is not
readily oxidised by chromic acid as the tertiary alcohol is highly oxidised. The chemical
equation for the above reaction is shown below:
3+ ¿+ H2 O ¿

Ethanol: 3 CH 3 CH 2 OH +2 CrO 4 +10 H +¿+3 CH CHO+2Cr

3 ¿

Isopropyl alcohol: 3 ¿

(ethanol equation with chromic acid - Bing images, 2019)

Hydrogen ions will be attracted to one of the oxygen atom in the chromic acid that is doubled
bonded to chromium. The lone pair electron from hydroxyl group of alcohol will attack the
chromium ion and form a chromate intermediate. The hydrogen on the hydroxyl group of
alcohol will leave as hydrogen ion and combine with oxygen atom that is previously attacked
by hydrogen ion. A water molecule will come and attack hydrogen on the alcohol and
produce hydronium ion, forming C=O double bond. Water molecule will leave the chromate
intermediate and the carbonyl product is formed. Since the oxidation of alcohol requires at
least one hydrogen atom to be presence on carbon, thus tertiary alcohol cannot be oxidised
because it does not have the hydrogen. This explains why t-butyl alcohol does not change the
colour of the chromic acid which is reddish brown.
The final test in this experiment is the reaction of sodium metal with alcohols. All the
alcohols able to react with sodium metal since all of them have –OH group. Based on Lewis
Bronsted Theory, Bronsted acid is a proton donor which donates H +¿¿ into the solution while
the sodium metal acts as strong base. A strong base can deprotonate the alcohol to yield an
alkoxide ion (R-O). The reaction between acid and base will produce hydrogen gas. This
evidence is shown by the release of colourless gas bubbles from the reaction between sodium
metal and alcohol. A pop sound is produced as the hydrogen gas is an explosive gas. Below is
the reaction equation of alcohols reacted with sodium metal:
2 C2 H 5 OH +2 Na2 C2 H 5 ONa + H 2

2 C3 H 7 OH +2 Na 2 C3 H 7 ONa + H 2

2 C 4 H 9 OH + 2 Na 2C 4 H 9 ONa+ H 2

The acidity of alcohol can be determined by the rate of gas evolution in the experiment. The
more the gas released, the more acidic the properties of alcohols. The acidity of alcohol
decrease as the number of carbon in bulky alkyl group that bonded to OH group increases.
Since, alkyl group is electron donating group, the more bulky the alkyl group, the stronger the
electron donor effect. Negative charge density in O atom and proton are less readily to
release. Moreover, bulky group are highly hydrophobic and tend to block the water molecule
from nearing the alcohol and stabilize it(Physical and chemical properties of alcohols, 2011). Hence,
the order of increasing acidity of alcohol is :
t-butyl alcohol < isopropyl alcohol < ethanol

Precautionary steps:
 Carry out all the above test in fume hood.
 Wear gloves during handle with chemicals
 Wear laboratory coat and goggles
 Discard the contents of any tube with unreacted sodium down the drain as
sodium reacts violently with water
 Add sufficient ethanol to destroy unreacted sodium
 All the chemical wastes in the experiment should be disposed carefully

Conclusion:
As a conclusion, ethanol, isopropyl alcohol, t-butyl alcohol, Unknown A and Unknown B are
soluble in water. For Lucas test, only t-butyl alcohol and Unknown B was reacted with Lucas
reagent except ethanol, isopropyl alcohol and Unknown A. For Chromic test, ethanol,
isopropyl alcohol and Unknown A was reacted with the chromic acid except t-butyl alcohol
and Unknown B. For the final test, reaction with sodium metal ethanol is more reactive
toward sodium metal compare to the isopropyl alcohol, t-butyl alcohol, Unknown A and
Unknown B. Hence, from the experiment the unknown alcohols were classified. Unknown A
is isopropyl alcohol whereas Unknown B is t-butyl alcohol. Besides, the alcohols were
classified into primary, secondary and tertiary alcohol too. From the experiment, it is shown
that the primary (1˚) alcohol is ethanol followed by secondary (2˚) alcohol which is isopropyl
alcohol and lastly tertiary (3˚) alcohol is t-butyl alcohol.
Reference:

an introduction to alcohols (2015) Chemguide.co.uk. Available at:

http://chemguide.co.uk/organicprops/alcohols/background.html (Accessed: March 15, 2019).

Physical and chemical properties of alcohols (2011) Blogspot.com. Available at:

http://1chemistry.blogspot.com/2011/05/properties-of-alcohol.html (Accessed: March 15, 2019).

UTAR WBLE KAMPAR CAMPUS: Login to the site (2019) Utar.edu.my. Available at: http://wble-
kpr.utar.edu.my/wble-kpr/file.php/18842/UDBB1164_Practical_Manual.pdf (Accessed: March 15, 2019).

Functional Groups - The Chromic Acid Test (2019) Harpercollege.edu. Available at:
http://dept.harpercollege.edu/chemistry/chm/100/dgodambe/thedisk/qual/chromic.htm (Accessed: March
15, 2019).

EXPERIMENT 4 (Organic Chemistry II) Pahlavan/Cherif (2008). Available at:

http://swc2.hccs.edu/pahlavan/2425L4.pdf (Accessed: March 15, 2019).

nucleophilic substitution images - Bing images (2019) Bing.com. Available at:

https://www.bing.com/images/search?
view=detailV2&ccid=3F96Ptm8&id=0C59708EC594DF6C9FCE90A10FAC5EA2C3594657&thid=OIP.3
F96Ptm8y47KSqBj6_mYNAHaFj&mediaurl=http%3A%2F%2Fslideplayer.com
%2F5790497%2F19%2Fimages%2F18%2FNucleophilic%2BAcyl
%2BSubstitution.jpg&exph=720&expw=960&q=nucleophilic+substitution+images&simid=60799809454
4866862&selectedindex=1&ajaxhist=0&vt=0 (Accessed: March 15, 2019).

ethanol equation with chromic acid - Bing images (2019) Bing.com. Available at:
https://www.bing.com/images/search?
view=detailV2&ccid=qd6IemuJ&id=1DD126FAE4269F3CDF9024A623477471C2EAA35C&thid=OIP.q
d6IemuJOR_cNc-zZIiZXQHaHx&mediaurl=http%3a%2f%2flh5.ggpht.com
%2f_VE77yZI3fI0%2fTcpUPS0h2mI%2fAAAAAAAAAYY%2f1qrlnFF_8j8%2fimage_thumb
%255B12%255D.png%3fimgmax
%3d800&exph=402&expw=383&q=ethanol+equation+with+chromic+acid&simid=607995886960839614
&selectedIndex=3&ajaxhist=0 (Accessed: March 15, 2019).