Classification of Alcohols

Purpose: In this experiment we will look at how to determine if an alcohol is

primary, secondary, or tertiary. Since the alcohols come in these three different
types it is important to distinguish between them.
Alcohols are very different from hydrocarbons due to the hydroxyl group
(OH) that is attached to the compound. This gives the organic compound very
different way of acting. The melting point and boiling point tend to be higher due to
the polar hydroxyl group which is capable of hydrogen bonding.. It also makes
alcohols more soluble in water. An example of this is ethanol, which is used for fuel,
is said to be miscible or mix with water in any ratio, which means that as a fuel it
must be handled with care so that water is not introduced. The key to solubility of
alcohols is the chain length of the hydrocarbon piece. The longer the chain the lower
the solubility is in water.
Alcohols are reactive and can be reduced to aldehydes, in primary alcohols, or
ketones, in the case of secondary alcohols. The primary alcohols if oxidized enough
will even become carboxylic acids. This will give a good indication as to whether the
alcohol as an known is primary, secondary, or tertiary since tertiary alcohols dont
undergo the oxidation of the carbon that they are attached to (remember that
tertiary alcohols have three carbons attached to the carbon with the hydroxyl
group).
In this experiment we will be determining the structure of the alcohol to
determine if it is primary, secondary, or tertiary by doing a series of reactions and
testing solubility. Most of the reactions will be oxidation reactions but there is one
reaction that can tell the substitution of the carbon that the hydroxyl group is on by
how long it takes to form the product. This is called the Lucas test, it is a
substitution reaction therefore the hydroxyl group has to act as a leaving group (as
water) and the carbocation is formed and then the substitution will happen on the
carbocation. Since the formation of the carbocation is so important in the
substitution reaction it becomes easy to tell which alcohol is primary, secondary, or
tertiary simply by how long it takes for the substitution reaction to occur. The
longer the time it takes to do the substitution the more likely it is that the alcohol is
primary. Remember that this is due to carbocation stability.
When performing a test to determine the structure of any compound it is
important to run the test on a known compound that will give a positive test and
another compound that will give a negative test. That is to say we want something
to compare an unknown to so that we have an idea of what our test is telling us.
Without the comparison we would often get results that are not clear which would
lead to assumptions of what the compound is that are incorrect. It is always
important to have the known tests to compare to.

Precautions:
Alcohols are flammable and should be handled with care and disposed of properly.
Lucas reagent is made with concentrated hydrochloric acid, which is corrosive.
Wash thoroughly if skin contact is made.
All work should be performed in the hood.
Procedure:
You will be assigned at least one test to perform for the known positive and the
known negative test as well as performing all tests on your unknown. You will
compare your results with the group or groups that performed the known positive
and known negative tests.
Solubility test
1. Write the identification code for your unknown on the space provided on
the data sheet.
2. Place 0.5 mL of each of the alcohols (ethanol, 2-propanol, 1-butanol, 2-
pentanol, 2-methyl-2-propanol, 1-octanol, and your unknown) in a small
test tube and add 1 mL of deionized water to it. Shake the contents of the
tube well to see if they mix. Record your observations on the data sheet,
this should be soluble, insoluble or slightly soluble.
3. Dump the contents of the tubes in the non halogenated waste container
and wash the test tubes with soap and water.
Ceric Nitrate Test
Ceric ammonium nitrate is used as a general test for the presence of the hydroxyl
group being present on an organic compound as long as the alcohol is soluble in
water. In the reaction you will be looking for the color to change from yellow to
orange red. In this test the hydroxyl group is modified to form a complex causing
the color change.
4. Pace 10 drops of the alcohols (ethanol, 2-propanol, and your unknown) in
separate test tubes. Add 10 drops of ceric nitrate solution to it. Record
your observations.
5. Discard the solutions in the non halogenated waste container and wash
the test tubes with soap and water.
Ferric Chloride Test for Phenols
Phenol reacts with iron (III) to go from a rust brown color to a pink or purple color.
6. Place 10 drops of the alcohols (ethanol, phenol, and your unknown) in
three test tubes. Add 10 drops of the 0.1 M FeCl3 solution to each test
tube. Record your observations.
7. Dump the contents of the tube in the halogenated waste container and
wash the test tubes with soap and water.
Structural Test
In this test you will be using chromic acid to oxidize the alcohol. Primary and
secondary alcohols will oxidize while tertiary alcohols will not. The change in
oxidation state for the chromium will yield a change in color from orange to blue
green.
8. Place 1 mL of the alcohols (ethanol, 2-propanol, 2-methyl-2-propanol,
and your unknown) in separate test tubes. Add to each tube 10 drops of
6M HCl, shake well. Add 1 to 2 drops fo 10 % Na2Cr2O7 amd shake the
mixture well again. Record your observations for each.
9. Dump the contents of the tube in the halogenated waste container and
wash the test tubes with soap and water.
Iodoform Test
In this test you will be using iodoform (CHI3) to test if the alcohol is primary,
secondary, or tertiary. The only primary alcohol that gives a positive test is ethanol,
all others will not. Secondary alcohols with the hydroxyl group on the carbon
number 2 will give a positive test but all other secondary alcohols will test negative
and tertiary alcohols have no reaction. A positive test gives a yellow precipitate and
the brown color diminishes where as a negative test has no precipitate. The alcohols
must be water soluble to perform this test.
10. Place 3 5 drops of each alcohol (ethanol, 1-propanol, 2-propanol, 2-
methyl-2-propanol, and your unknown) in different test tubes. Dilute
with 2 mL of water and mix well. Add 2 mL of 3 M NaOH and mix well
again. Add 3 mL of the iodine solution to the mixture and mix well once
more. Record yoru observations for each.
11. Dispose of the content of the tube in the Halogenated Waste container.
Wash the test tube with soap and water.
Lucas Test
12. Add 1 mL of each alcohol (ethanol, 2-propanol, 2-methyl-2-propanol, and
your unknown) to different test tubes. Add 10 mL of the Lucas reagent to
each tube and shake to mix well. Measure the amount of time that is
needed to form a cloudy layer. If there if no reaction in 15 minutes you
should be able to consider it a primary alcohol. Record your observations
and times on the data sheet.
13. Dispose of the content of the tube in the Halogenated Waste container.
Wash the test tube with soap and water.
Data:
Unknown code: _____________________________
Solubility Test
Alcohol Water solubility

ethanol

2-propanol

1-butanol

2-pentanol

2-methyl-2-
propanol

1-octanol

Unknown
Ceric Nitrate Test
Alcohol Observations

ethanol

2-propanol

unknown

Ferric Chloride Test

Alcohol Observations

ethanol

phenol

unknown
Chromic Acid Tests
Alcohol 1o, 2o, 3o, ? Observation

ethanol

2-propanol

2-methyl-2-propanol

unknown

Iodoform Test
Alcohol Observation

1-propanol

2-propanol

ethanol

2-methyl-2-propanol

unknown
Lucas Test
Alcohol 1o, 2o, 3o, ? Observations

ethanol

2-propanol

2-methyl-2-propanol

unknown

Describe the unknown in terms of what you are able to determine from the tests.
Post lab questions
1. An alcohol is oxidized by chromic acid and does not react with Lucas
reagent. What class of alcohol is it? Explain your answer.

2. Draw the structure of 2-methyl-2-pentanol. Predict the results of the

following test.

a) Chromic acid test

b) Lucas test

c) Iodoform test

3. What is your unknown, a primary, secondary, or tertiary alcohol?

Pre lab questions: You may need to use your text book or the internet to find all
of the answers for questions below.
1. What is the functional group that determines if a compound is an alcohol?

2. What observation is for a positive iodoform test?

3. Name and draw an example of a primary, secondary, and tertiary alcohol.

4. What factor is associated with the increase in boiling point of alcohols?

5. What factor is associated with the increase in solubility of alcohols?