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Classification Tests for Hydroxyl- and Carbonyl- Containing Compounds

Introduction and Procedure:


A chemical test is a qualitative or quantitative procedure designed to prove the existence of, or to quantify, a chemical
compound or chemical group with the aid of a specific reagent. The following tests were conducted to distinguish
whether hydroxyl or carbonyl containing, to identify the type of alcohol it contains, to determine if aldehyde or
ketone and to explain the mechanisms involved.
Due to the limited availability of chemicals, only the following tests were conducted:
1. Solubility of Alcohol in Water
Most organic molecules are relatively non-polar and are usually soluble in organic solvents (e.g. diethyl ether,
dichloromethane, chloroform, petroleum ether, hexanes etc.) but not in polar solvents like water. However, some
organic molecules are more polar and therefore soluble in water. This denotes a rather high ratio of polar group(s) to
the non-polar hydrocarbon chain, i.e., a low molecular weight compound containing an -OH, -NH
2
or -CO
2
H group, or a
larger molecule containing several polar groups.

2. Chromic Acid Test (Jones Oxidation)
The orange-yellow Jones reagent will immediately turn green in the presence of 1 and 2 alcohols and aldehydes. The
color change is typically observed only for these functional groups and this color change constitutes a positive result.
Tertiary alcohols do not react with Jones reagent. Sometimes amines, ethers, ketones, alkenes and alkynes will give a
positive test after 2-5 seconds due to contamination with alcohols.

3. 2,4-dinitrophenylhydrazone (or 2,4-DNP) Test
2,4-Dinitrophenylhydrazine can be used to qualitatively detect the carbonyl functionality of a ketone or aldehyde
functional group. A positive test is signaled by a yellow, orange or red precipitate. If the carbonyl compound is aromatic,
then the precipitate will be red; if aliphatic, then the precipitate will have a more yellow color.

Label 3 test tubes and add 10 drops of ethanol, sec-
butyl alcohol and tert-butyl alcohol in each using a
Pasteur pipette.
Add 1-mL of water dropwise to the test tube
containing the alcohol, shaking the mixture
throughly in each addition.
If cloudiness results, continue adding 0.25-mL water
at each time with vigorous shaking until
homogeneous dispersion results.
Note the total volume of water. If no cloudiness
results after the addition of 2.0-mL water, the
alcohol is soluble in water. Note down the results.
Dissolve a drop of liquid sample in
1-mL acetone in a test tube.
Add 5 drops of Jones reagent.
Perform test on n-butyl alcohol,
tert-butyl alcohol and acetone.
Place a drop of sample into a small test tube. Add 5 drops of 95% ethanol and shake well.
Add 3 drops of 2,4-dinitrophenylhydrazine. If no
yellow or orange-red precipitate forms, allow the
solution to stand for at least 15 minutes.
Perform the test with acetone and acetaldehyde.
Classification Tests for Hydroxyl- and Carbonyl- Containing Compounds
Discussion of Results:
The term hydroxyl group is used to describe the functional group OH when it is a substituent in an organic
compound . Organic molecules containing a hydroxyl group are known as alcohols, the simplest of which have the
formula C
n
H
2n+1
OH.
Hydroxyl groups are especially important in biological chemistry because of their tendency to form
hydrogen bonds, both as a donor and acceptor, which are related to their ability to
increase hydrophilicity and water solubility.
Alcohol Structural Formula
mL H
2
O needed to produce
homogeneous dispersion
Solubility in water
ethanol

1-mL Miscible
n-butyl alcohol

1-mL Miscible
tert-butyl alcohol

9-mL Miscible

Two opposing solubility trends in alcohols are: the tendency of the polar -OH to promote solubility in water, and the
tendency of the carbon chain to resist it. Thus, ethanol, and n-butyl alcohol are miscible in water because the hydroxyl
group wins out over the short carbon chain while the miscibility of tert-butyl is decreased.
As seen from the structure, n-butyl alcohol is a four carbon straight chain with the hydroxyl group at the end. The
ratio of four carbons exposed to only one -OH group exposed limits the solubility of the straight chain. Carbons chains are
more in line with the alkanes and are more miscible with oils than water. On the other hand the tert-butyl alcohol has
the OH group right in the middle of the chain and tends to shield the carbons more and makes the -OH group more
accessible to mixing with water and therefore more soluble.
Alcohols with one to three carbons are miscible in any polar solvent. The miscibility of alcohols with more than
four carbons starts to decrease, whereas those with more than seven carbons are considered immiscible.

Structural Formula Chromic Acid Test
n-butyl alcohol

Oxidized; green precipitate forms
tert-butyl alcohol

Not oxidized; precipitate forms
acetone

Not oxidized; precipitate forms

Alcohols are classified into primary (1), secondary (sec-, s- or 2), and tertiary (tert-, t- or 3), based upon
the number of carbon atoms connected to the carbon atom that bears the hydroxyl functional group.
Classification Tests for Hydroxyl- and Carbonyl- Containing Compounds
While a carbonyl group is a functional group composed of a carbon atom double-
bonded to an oxygen atom, C=O.
The Jones reagent is chromium trioxide (CrO
3
) in sulfuric acid (H
2
SO
4
). It is a potent
oxidizing agent which rapidly oxidizes primary alcohols and aldehydes to carboxylic
acids, and secondary alcohols to ketones.
Alcohols react with the yellow-orange Jones reagent containing a Cr (VI) atom. Over
the course of the organic oxidation, the Cr is reduced to Cr (III). The first two steps of
the reaction mechanism help to explain why tertiary alcohols do not undergo oxidation with the Jones reagent. In step 2,
water reacts with a proton of the chromate ester that is bonded to the carbon atom of the former alcohol functional
group. Tertiary alcohols do not have a hydrogen atom bonded to this carbon; therefore the reaction could not proceed
beyond this point.
a. Summarization of Jones Oxidation with primary and secondary alcohols


b. Jones Oxidation Mechanism on primary alcohols




Classification Tests for Hydroxyl- and Carbonyl- Containing Compounds

c. Jones Oxidation Mechanism on secondary alcohols



Thus, n-butyl alcohol, being a primary alcohol, is oxidized indicated by the formation of a Cr
3+
ion, having a color green
appearance, whereas tert-butyl alcohol is not oxidized, being a tertiary alcohol. And acetone, as well, is not oxidized,
being typically used as the organic solvent.

Structural Formula 2,4-DNP Test
Acetaldehyde

Positive; orange
Acetone

Positive; yellow
Classification Tests for Hydroxyl- and Carbonyl- Containing Compounds

Carbonyl groups are common to several classes of organic compounds, as part of
many larger functional groups, aldehydes (characterized by the presence of a
carbonyl functional group at the end of a compound's carbon skeleton) and ketones
(a type of organic compound where a carbonyl group bonds to two other carbon
atoms of the carbon backbone) for example.
2,4-dinitrophenylhydrazine is often abbreviated to 2,4-DNP or 2,4-DNPH.
A solution of 2,4-dinitrophenylhydrazine in a mixture of methanol and
sulfuric acid is known as Brady's reagent.
R and R' can be any combination of hydrogen or hydrocarbon groups
(such as alkyl groups). If at least one of them is hydrogen, then the
original compound is an aldehyde. If both are hydrocarbon groups, then it
is a ketone.


The reaction is known as a condensation reaction, one in which two molecules join
together with the loss of a small molecule in the process. In this case, water. In
terms of mechanisms, it is a nucleophilic addition-elimination reaction wherein 2,4-
dinitrophenylhydrazine is first added across the carbon-oxygen double bond (the addition stage) to give an intermediate
compound and then lose a molecule of water (the elimination stage).

Hence, acetaldehyde is an example of aldehyde, thus has a positive result. The same goes to acetone, being a ketone.

Summary and Conclusion:
There are different types of tests to classify unknown compounds. The simplest examples include solubility in
water to determine the polarity of a compound; chromic acid test to distinguish primary and secondary alcohols by
oxidation to produce aldehydes and ketones through the appearance of green chromium (III) ion; and 2,4-
dinitrophenylhydrazine test to differentiate aldehydes and ketones from other compounds by the presence of yellow to
red precipitate.
Thus, organic compounds can be identified and classified through similarities within its structure and properties
shown by chemical tests.

PRE-LAB ASSIGNMENT
1. Differentiate the three types of alcohol. Give an example for each.
Alcohols are classified into primary (1), secondary (sec-, s- or 2), and tertiary (tert-, t- or 3), based upon the number of
carbon atoms connected to the carbon atom that bears the hydroxyl functional group.


Classification Tests for Hydroxyl- and Carbonyl- Containing Compounds

Type Definition Example
Primary
Alcohols in which the carbon carrying the -OH
group is only attached to one alkyl group
1-propanol

Secondary
Alcohols in which the carbon carrying the -OH
group is attached to two alkyl group which
may be the same or different
2-butanol

Tertiary
Alcohols in which the carbon carrying the -OH
group is attached to three alkyl group which
may be the combination of same or different
2-methyl-2-propanol


2. Differentiate aldehydes from ketones based on chemical structure.
Definition Structure
Aldehyde
A type of organic compound where a carbonyl
functional group is at the end of the carbon
skeleton

Ketone
A type of organic compound where a carbonyl
functional group bonds two other carbon atoms of
the carbon backbone


POST LAB ASSIGNMENT
1. How do structure and number of carbons affect the solubility of alcohols in water?
The physical properties of alcohols are influenced by the hydrogen bonding ability of the -OH group. The longer the
carbon chain in an alcohol is, the lower the solubility in polar solvents and the higher the solubility in nonpolar
solvents.
2. Based on the samples used, which alcohol is most readily oxidized? Why do you think so?
Out of three samples tested, n-butyl alcohol is most readily oxidized because of
being an example of a primary alcohol.