CLASSIFICATION TESTS FOR HYDROXYL- AND CARBONYL-CONTAINING COMPOUNDS

Pia Lorraine F. San Luis, Michelle Joy G. Sia, Paulene Stephanie A. Soriano,
Trisha Joy M. Taas, Lara Monique S. Tuazon and Michelle V. Yu
Group 8 2C Biochemistry Organic Chemistry Laboratory

ABSTRACT
This experiment aimed to distinguish whether a compound is hydroxyl- or carbonyl-containing. This
is done to differentiate the three types of alcohols and differentiate aldehydes from ketones. It also aimed
to explain the mechanisms involved in the differentiating tests. In this experiment, there are several
differentiating tests done using different samples such as: n-butyl alcohol, sec-butyl alcohol, tert-butyl
alcohol, Acetaldehyde, n-butyraldehyde, Benzaldehyde, Acetone, Acetophenone and Isopropyl alcohol. The
tests include the following: solubility of alcohols in water, Lucas test, Chromic Acid Test (Jones Oxidation),
2,4-dinitrophenylhydrazone (or 2,4-DNP) Test, Fehlings Test, Tollens Silver Mirror Test and Iodoform Test.
In the solubility of alcohols in water n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol were miscible in
water and only benzzyl alcohol was immiscible. Using Lucas test to differentiate the primary, secondary,
and tertiary alcohols, there was no change in n-butyl alcohol and the solution turns turbid in both sec-
butyl alcohol and tert-butyl alcohol. Moreover, the turbidity is due to the alkyl chloride formation. The
Chromic Acid Test is for compounds that possess oxidizing or reducing property and in the experiment, no
change in color happened in the test samples. In 2,4-DNP Test, conducted as confirmatory tests for
carbonyl groups and gave results of yellow orange precipitate for acetaldehyde and acetone, orange
precipitate for benzaldehyde, and orange red precipitate for acetophenone. Fehlings Test and Tollens
Silver Mirror Test are both conducted to differentiate aldehydes and ketones. In Fehlings Test, there was
no change in the blue solution of Ketone while the blue solution of Aldehyde gives a positive result of a
brick red precipitate of cuprous oxide. On the other hand, in Tollens Silver Mirror Test, there was no
change in the colorless solution of benzaldehyde and acetophenone while the colorless solution of
acetaldehyde and acetone produces a silver mirror on the test tube. Lastly, Iodoform test gives a positive
result of a yellow precipitate only in acetone and isopropyl alcohol.

INTRODUCTION two (different or similar) alkyl groups. While

tertiary alcohols are alcohols attached directly to
Alcohol is one of the most common organic three alkyl groups. [2]
compounds, they are widely used in different
industries. It is a compound that has a hydroxyl
group bonded to a saturated sp 3-hybridized
carbon atom, R-OH. Alcohols are polar because of
the hydroxyl group which allows alcohol to attract
other molecules through hydrogen bonding which
is related to their ability to increase water
solubility. [1]

Figure 2. Types of alcohol.

Figure 1. Structure of
alcohols.
Aldehyde is a carbonyl-functional group that is
bonded to a hydrogen atom while a ketone is a
functional group that is bonded to two carbon
Alcohols can be classified as primary,
atoms. Both functional groups are polar that
secondary or tertiary depending on how the
interacts with dipole-dipole interaction. This
hydroxyl group (-OH) is bonded to the carbons.
results to a higher boiling point than those
Primary alcohols are alcohols in which the -OH is
nonpolar compounds. [3]
bonded to a single alkyl group; on the other
hand, secondary alcohols are attached directly to
 Lucas test, Chromic Acid Test, 2,4-DNP test, acidic and will react with base to form the anion,
Fehlings Test,Tollens Silver Mirror test and which then reacts with iodine to form an alpha-
Iodoform test were the test used in the iodo ketone. In a methyl ketone, all three alpha
experiment. hydrogens are substituted by iodine in this way
to form the triiodo compound, which then reacts
Lucas reagent is a solution of concentrated with more base to form the carboxylic acid salt
hydrochloric acid and anhydrous zinc chloride. plus iodoform, a yellow precipitate. Formation of
This is used as a reagent in Lucas test. This test a yellow precipitate therefore indicates the
is used to determine the type of alcohol based on presence of a methyl group directly attached to
reactivity. The reaction that occurs in the Lucas the carbonyl. [6]
test is an SN1 nucleophillic reaction. The acid
catalyst activates the OH group of the alcohol by EXPERIMENTAL
protonating the oxygen atom. The bond breaks to
generate a carbocation cation which in turns A. Samples used
reacts to chloride forming an alkyl halide product. The samples used in the experiment were
[4] ethanol, n-butyl alcohol, sec-butyl alcohol, tert-
The chromic acid test is a test for primary, butyl alcohol, benzyl alcohol, n-butyraldehyde,
secondary alcohols and aldehyde. A blue-green benzaldehyde, acetone, acetophenone, isopropyl
layer indicates a positive test. In this test, alcohol, and acetaldehyde.
primary alcohols and aldehyde are oxidized to B. Procedure
carboxylic acids while alcohols are oxidized to
ketones and the Cr6+ ions are reduced to Cr3+. [5] 1. Solubility of Alcohols in Water

The 2,4-dinitrophenylhydrazone test is Five test tubes were labeled (A-E), and 10 drops
performed to determine the presence of a of each alcohols (A-ethanol, B-n-butyl alcohol, C-
carbonyl group(ketone and aldehyde). It is also a sec-butyl alcohol, D-tert-butyl alcohol, and E-
derivative formation. It reacts to form a solid 2,4- benzyl alcohol) were placed. 1 mL of water one
dinitrophenylhydrazone (DNP) derivative. The drop at a time was added to each tube containing
color imparted gives us a structural information. the alcohols and the mixture was shaken
Positive result for this test is the formation of thoroughly after each addition. 0.25 mL of
yellow orange precipitate. If the precipitate distilled water was added at a time with vigorous
produced is yellow, it means that the carbonyl shaking when cloudiness was observed. The total
group in the unknown is unconjugated. A volume of water added was noted. The solubility
reddish-orange color most likely means that the of alcohol in water was determined by observing
carbonyl group is conjugated. [6] the results after adding 2.0 mL water.

Fehlings test uses the fehlings solution,a 2. Lucas Test

mixture of Fehlings A (copper(II) sulfate) and
Preparation of the reagent was not needed,
Fehlings B (sodium potassium tartate and
because it was already prepared. About 50 mg
sodium hydroxide), which is an oxidizing agent.
(2-3 drops) of sample was added to 1 mL of the
Only aldehydes are oxidized to carboxylic acids
reagent in a small vial. The vial was capped and
and will reduce the cupric ion to cuprous oxide. A
shook vigorously for a few seconds. The mixture
positive result produces a brick red precipitate.
was allowed to stand at room temperature. This
[7]
test was performed on n-butyl alcohol, sec-butyl
Tollens test uses the Tollens reagent alcohol, and tert-butyl alcohol. Formation of
(Ag(NH3)2+ /OH- is a weak oxidant only aldehydes cloudy suspension or formation of 2 layers was
will react in this test. Aldehydes will be oxidized observed.
to caboxylic acids. As a result, it will produce a
3. Chromic Acid Test (Jones Oxidation)
silver mirror which is the positive result. [7]
The iodoform test indicates the presence of an Preparation of the reagent was not needed,
aldehyde or ketone in which one of the groups because it was already prepared. 1 drop of the
directly attached to the carbonyl carbon is a liquid sample was dissolved in 1 mL of acetone in
methyl group. In the iodoform test, the unknown a small vial. 5 drops of chromic acid reagent were
is allowed to react with a mixture of iodine and added, one drop at a time, while shaking the
base. Hydrogens alpha to a carbonyl group are mixture. The test tubes were placed in 60 C
water bath for 5 minutes. The color of each For the test for solubility of alcohols in
solution was noted. water, the turbidity of the solutions was
observed. The cloudiness of the solution means
4. 2,4-dinitrophenylhydrazone (or 2,4-DNP) that the specific alcohol is soluble in water. The
Test amount of water needed to produce a
Preparation of the reagent was not needed, homogenous dispersion was also recorded.
because it was already prepared. Drops of the Table 1. Solubility of Alcohols in water.
liquid samples were placed into five different test
tubes. 5 drops of 95% ethanol was added to Amount
each. It was well shook. 3 drops of 2,4- of water Solubil
dinitrophenylhydrazine was added. The solutions Alcohol needed ity in
were allowed to stand for 15 minutes when no to water
produce
yellow/orange-red precipitate was formed. This
a
test was performed on acetaldehyde, homoge
benzaldehyde, acetone, and acetophenone. The nous
results were described. dispersi
on
5. Fehling's Test
Ethanol 1 drop miscibl
Reagent was made by mixing equal amounts of
CH3CH2OH e
Fehling's A (7 g of hydrated copper (II) sulfate
dissolved in 100 mL of water) and Fehling's B (35
n-butyl alcohol 61 drops miscibl
g of potassium sodium tartrate and 10 g of NaOH e
in 100 mL water). 1 mL of freshly prepared
Fehling's reagent was placed into each test tube.
sec-butyl
3 drops of sample was added to be tested. The alcohol 20 drops miscibl
test tubes were placed in a beaker of boiling e
water and the changes occurred were observed
within 10-15 minutes.Tthis test was performed
on acetaldehyde, benzaldehyde, acetone, and
acetophenone. The results were described.
tert-butyl
6. Tollens Silver Mirror Test alcohol 4 drops miscibl
e
Preparation of the reagent was not needed,
because it was already prepared. Four test tubes
with 1 mL of freshly prepared Tollens reagent Benzyl alcohol
were prepared. Two drops of each sample were
added separately: acetaldehyde, benzaldehyde, 3 mL immisci
acetone, and acetophenone. The mixtures were ble
shook and were allowed to stand for 10 minutes.
The test tubes were placed in a beaker of warm
water (35-50 C) for 5 minutes. Observations
were recorded. As shown in the table above, only benzyl
alcohol was insoluble in water while ethanol, n-
7. Iodoform Test butyl alcohol, sec-butyl alcohol, tert-butyl alcohol
were all soluble. This follows the principle "like
Two drops of each sample (acetaldehyde,
dissolves like" and therefore it can be said that
benzaldehyde, acetone, acetophenone, and
the alcohols soluble in water were polar
isopropyl alcohol) were placed into its own test
compounds.
tube. 20 drops of 10% KI solution was added.
While shaking, 20 drops of fresh chlorine bleach The Lucas test differentiated three
(5% sodium hypochlorite) was added and mixed samples namely n-butyl alcohol, sec- butyl
in each tube. Formation of a yellow precipitate alcohol, and tert-butyl alcohol. Table 2 presents
was noted. the results of the Lucas test.

RESULTS AND DISCUSSION

 As indicated in the table, acetaldehyde
and acetone produced a yellow orange
Table 2. Lucas Test. precipitate, benzaldehyde produced an orange
Substance Reaction observed precipitate, and only acetophenone produced a
red orange precipitate which indicated the
n-butyl alcohol no changes presence of a carbonyl group. Below is the
chemical equation for this test:

sec-butyl alcohol turbid

tert-butyl alcohol turbid

According to the table above n-butyl

alcohol is soluble in Lucas reagent while a The Fehling's test and Tollen's Silver
formation of a cloudy layer was observed in sec- mirror test were performed to differentiate
butyl alcohol and tert-butyl alcohol. Below is the aldehydes from ketones. In the Fehling's test,
chemical equation for this test: aldehydes gave a positive result of brick red precipitate
while ketones did not produce any reaction. In the Tollen's
test, aldehydes were expected to be oxidized while ketones
did not undergo any oxidation.

Table 3. Fehling's Test and Tollen's Silver Mirror Test

The Chromic Acid Test is a test for Substance Fehling's Tollen's

compounds containing oxidizing or reducing Acetaldehyde brick red silver mirror
property. No color changes in all the samples precipitate precipitate
were observed by the analysts. Below is the Benzaldehyde no precipitate no precipitate
Acetone no precipitate silver mirror
chemical equation for this test:
precipitate
Acetophenone no precipitate no precipitate

As shown in the table above, only

acetaldehyde produced a brick red precipitate
and in the Tollen's test the acetaldehyde and
acetone produced a silver mirror precipitate.
Below are the chemical equations for these tests:

Fehling's test

The 2,4-dinitrophenylhydrazone (or 2,4-

DNP) Test was a confirmatory test for the
presence of carbonyl groups. The formation of a Tollen's test
red orange precipitate gives a positive result.

Table 2. 2,4-DNP Test.

Substance Color of Precipitates

Acetaldehyde yellow orange
Benzaldehyde orange
Acetone yellow orange
Acetophenone red orange
In the Iodoform test methyl ketones gave
a positive iodoform test.
 [3] Aldehydes and Ketones - Dufferin-Peel
Catholic District ... (n.d.). Retrieved November
20, 2016, from
Table 4. Iodoform test. http://www.dpcdsb.org/NR/rdonlyres/9B6E4EF6-
77F0-407F-A858-
Substance Reaction observed F0DF78B6896C/101655/15AldehydesandKetones.
Acetaldehyde no yellow precipitate pdf
n-butyraldehyde no yellow precipitate
Benzaldehyde no yellow precipitate [4] (n.d.). Retrieved November 20, 2016, from
Acetone yellow precipitate http://www.chemistrylearner.com/lucas-
Acetophenone no yellow precipitate
reagent.html
Isopropyl alcohol yellow precipitate

According to the given table, only acetone [5] Functional Groups - The Chromic Acid Test.
and isopropyl alcohol produced a yellow (n.d.). Retrieved November 20, 2016, from
precipitate. Below is the chemical equation for http://www.harpercollege.edu/tm-
this test: ps/chm/100/dgodambe/thedisk/qual/chromic.ht
m

[6] Identification of an Unknown Alcohols,

Aldehydes, and ... (n.d.). Retrieved November
20, 2016, from
http://www.chem.umass.edu/~samal/269/aak.pd
f
REFERENCES
[7] Writer, B. (1970). Reactions of Aldehydes,
[1] Alcohol. (n.d.). Retrieved November 20,
Ketones And Phenols. Retrieved November 20,
2016, from
2016, from
https://www.britannica.com/science/alcohol
http://1chemistry.blogspot.com/2011/09/reactio
[2] An introduction to alcohols. (n.d.). Retrieved ns-of-aldehydes-ketones-and.html
November 20, 2016, from
http://chemguide.co.uk/organicprops/alcohols/ba
ckground.html