CLASSIFICATION TESTS FOR HYDROXYL- & CARBONYL CONTAINING COMPOUNDS

Pabustan B. Isabella, Paris C. Amanda, Publico S. Helen,

Quintero B. Hannah, Ramirez M. Kesney, Ramos I. Patricia Kaye
Group 6 1E Medical Technology Inorganic and Organic Chemistry Laboratory

ABSTRACT
In organic chemistry, hydroxyl and carbonyl groups are examples of functional groups that can be
attributed to the characteristic of different molecules and in this experiment, various differentiating tests
were conducted to distinguish the given samples from one another. The solubility test in water for alcohols
was conducted to differentiate the solubility of different alcohol samples which yielded a result that
indicated n-butyl alcohol and benzyl alcohol as immiscible in water and ethanol, sec-butyl alcohol, and
tert-butyl alcohol as all miscible in water. Meanwhile, in ester formation, various odors, such as rum,
sweet odor, banana, orange, and pineapple were produced by synthesizing esters from carboxylic acid
mixed with different types of alcohols. In the Lucas test, 1°, 2°, and 3° alcohols were differentiated from
one another and the results indicated a positive result for turbidity as observed in the tert-butyl alcohol as
well as the rate of reaction in the different alcohol samples tested with n-butyl alcohol being the least
reactive. Lastly, the chromic acid test was used to identify oxidizable carbons wherein a blue-green
solution was produced by the sec-butyl alcohol, n-butyl alcohol, and acetaldehyde to indicate a positive
result.

INTRODUCTION can be used as solvents as well [8]. Examples of

Hydroxyl group is a functional group composed
of two atoms, namely oxygen and hydrogen,
which are covalently bonded to each other [1]. It
is shown in chemical structures as “-OH” and has
a valence charge of -1 [1]. It can be very
reactive when combined with other chemicals
[1]. Hydroxyl groups can be found in sugars and
alcohols [2]. On the other hand, carbonyl group
is a functional group which has a carbon that is
double bonded to an oxygen (C=O) [3].
Aldehydes and ketones are the simple forms of
carbonyl group [3]. Aldehydes contain a carbonyl
group bonded to a hydrogen atom and another
carbon atom while ketones contain a carbonyl
group and two carbon atoms [4]. Moreover,
aldehydes tend to be more reactive than ketones
because the carbon in the carbonyl group of
aldehydes have a more partial positive charge
than in ketones [5]. These carbonyl groups are
important for giving the smell and taste of
aromatic compounds [3].
An alcohol always consists of a carbon chain
and an OH group [6]. In cases of alcohols, the
solubility rule “like dissolves like” applies [6].
Alcohols are soluble in water because of the
hydroxyl group in the alcohols which can form
hydrogen bonds with water [7]. Alcohols with a
shorter hydrocarbon chain are more soluble than
the ones with the longer chains [6].
Esterification happens when alcohols react with
carboxylic acids resulting to water and ester
formation [9]. This process is a condensation
reaction wherein two molecules combine and
produce a larger molecule while removing the
smaller one [8]. Esters are soluble in water [10].
They are mostly used for flavour, perfumes and
esters are fats and oils found in our usual diets
[8].
The Lucas test helps in differentiating the
different types of alcohol which are the primary,
secondary, and tertiary alcohol [11]. It makes
use of the Lucas reagent which reacts with the
alcohol to produce a turbid solution [11]. It
differentiates the different types of alcohol based
on how long the turbid solution will be produced
[11]. The reaction between the Lucas reagent
and the alcohol is a SN1 substitution reaction
wherein the chloride from the zinc chloride of the
Lucas reagent gets substituted by the hydroxyl
group [11].
Chromic acid is one of the reagents commonly
used to show oxidation in organic chemistry [12].
It is a strong acid used to oxidize alcohols to
carboxylic acids and ketones [12]. Chromic acid
can oxidize primary alcohols to carboxylic acids,
secondary alcohols to ketones, and aldehydes to
ketones [13]. This test uses Jones reactant that
results to color change in aldehydes and alcohols
[12].
This experiment aims to determine if the
sample used contains hydroxyl or carbonyl. It
also aims to identify the three types of alcohol
and tell apart aldehydes from ketones. By being
able to identify these chemical structures, the
chemical equations and the mechanisms involved
in the reactions can be explained.
EXPERIMENTAL
A. Samples used
Ethanol, n-butyl alcohol, sec-butyl alcohol, tert-
butyl alcohol, benzyl alcohol, ethyl alcohol,
isopentyl alcohol, octyl alcohol, formic acid, acetic
acid, propionic acid, n-butyraldehyde, separate vials each containing 10 drops of
benzaldehyde, acetone, and acetophenone acetone. After dissolving the substances in the
acetone, 2 drops of 10% K2Cr2O7(aq) were placed
B. Procedure in each vial and finally 5 drops of 6M H2SO4 were
Solubility for Alcohols in Water then added. The change in color of the mixtures
The miscibility of the different alcohol from red-orange to blue-green was observed in
samples in water was tested with 10 drops each some mixtures which indicated that oxidation was
of ethanol, n-butyl alcohol, sec-butyl alcohol, present.
tert-butyl alcohol, and benzyl alcohol that were
placed, by means of a Pasteur Pipette, into five RESULTS AND DISCUSSION
test tubes labelled accordingly. 1.0 mL of water
was added to each test tube and shook Solubility for Alcohols in Water
rigorously. An opaqueness in the mixture was An alcohol’s solubility is inversely proportional
observed thereafter in some mixtures. When to the length of its hydrocarbon chain which
these mixtures turned opaque, the continuous means that the longer the hydrocarbon chain
addition of 0.25 mL of water to the mixture there is to an alcohol, the more insoluble it gets
before shaking it thoroughly produced a [14].
homogenous dispersion or a clear appearance, Meanwhile, the solubility of isomeric alcohols in
however some mixtures maintained their opaque water, such as tert-butyl alcohol, is directly
appearance. The disappearance of some of the proportional with its branching due to its surface
mixture’s opaqueness before or even right after area decreasing [15].
2.0 mL of water was added into the mixture
indicated that the sample was miscible in water. Table 1. Solubility of Alcohols in Water
Sample Condensed Amount of Solubility
Ester Formation Structural Water (mL) in Water
In ester formation, 10 drops of carboxylic acid Formula added to
produce a
and 10 drops of alcohol were placed into a test
homogenous
tube, before adding 4 drops of conc. H2SO4. In a dispersion
250.0 mL beaker, 150.0 mL of tap water was Ethanol CH3CH2OH 1 mL Miscible
poured before immersing the test tube in the N-butyl CH3CH2CH2CH2 2.5 mL Immiscibl
beaker. By means of a hot plate, water was alcohol OH e
heated to a temperature of approximately 60°C. Sec- CH3CHOHCH2 C 1.25 mL Miscible
After 15 minutes of immersing the test tube in butyl H3
the water bath, it was put in another beaker filled alcohol
with cold water. After allowing it to cool, 5.0 mL Tert- (CH3)3 COH 1 mL Miscible
of distilled water was placed into the test tube. butyl
alcohol
Odor produced by the ester was observed by
Benzyl 6 mL Immiscibl
holding it at a distance of 30cm from the nose.
alcohol e

Lucas Test
To determine the differences in reactivity
among alcohol derivatives, 2-3 drops of n-butyl
alcohol, sec-butyl alcohol and tert-butyl were
placed in 3 separate test tubes with 1.0 mL of
Lucas reagent (16.0 g of anhydrous zinc chloride
with 10.0 mL conc. HCl). Each vial was shaken
vigorously and then placed in room temperature. Figure 1. Test for solubility of alcohols in water.
The reactivity of the n-butyl alcohol, sec-butyl (a) ethanol; (b) n-butyl alcohol; (c) sec-butyl
alcohol and tert-butyl alcohol with the Lucas alcohol; (d) tert-butyl alcohol; (e) benzyl alcohol.
reagent is determined by its turbidity. Some
solutions remained colorless while some had a Ethanol, sec-butyl alcohol, and tert-butyl
cloudy second layer formation or emulsion. alcohol were all miscible in water while n-butyl
alcohol and benzyl alcohol were immiscible in
water as indicated by their opaque appearance
Chromic Acid Test even after the addition of 2.0 mL of water.
To test for the oxidation of certain substances, Ethanol has two hydrocarbon chains, so it is
1 drop of n-butyl alcohol, sec-butyl alcohol, tert- the most soluble in water compared to other
butyl alcohol, n-butyraldehyde, benzaldehyde, samples. It is followed by tert-butyl alcohol and
acetone, and acetophenone were dissolved in
sec-butyl alcohol respectively since tert-butyl alcohol
alcohol has more branching substituents than the
latter. N-butyl alcohol was considered immiscible Propionic Ethyl Ethyl Pineapple
compared to the other two butanol derivatives Acid alcohol propanoate
since it has the least branching substituents.
Meanwhile, the benzyl alcohol was also
considered immiscible due to the non-polarity of The table indicates the esterification of
its benzene ring [16]. carboxylic acids such as formic acid, acetic acid,
and propionic acid, with alcohols namely ethyl
Ester Formation alcohol, isopentyl alcohol, octyl alcohol, and ethyl
In order to observe the odor produced by the alcohol. It also shows the ester formed as well as
esters formed, carboxylic acid and alcohols were the odor it produced.
heated together in the presence of a catalyst,
usually a few drops of concentrated sulfuric acid.
Esters commonly form a thin layer on the
surface since they are insoluble in water (except
for the very small ones) [17]. Alcohol and the
excess acid are dissolved together and stays
beneath the layer of ester [17].

Figure 3. Octyl Figure 4.

Acetate Ethyl Acetate
Source: Lozano, D. (2014 March, 18). Ester
synthesis lab report. Retrieved from
https://www.youtube.com/watch?v=RdtaLRw1N
wI
Figure 2. Ester formation of acetic acid and ethyl
alcohol. Lucas Test
The classification of alcohols in the Lucas test is
In the figure above, the carboxylic acid used based on the different reactions with
was acetic acid and the alcohol used was ethyl concentrated hydrochloric acid that is present in
alcohol. Due to the esterification of acetic acid the reagent. The reagent and alcohols undergo a
and ethanol, ethyl acetate was synthesized. Upon substitution reaction where the chloride in
the addition of water to the compound, after its anhydrous zinc chloride (which acts as the
water bath and cooling, the odor it produced was catalyst) is replaced by the hydroxyl group of the
a sweet smell. The same type of reaction, alcohols. This test is only applicable for alcohols
although with a different odor, could be observed which are soluble in Lucas reagent or alcohols
with the different type of samples upon that contain six or less carbon atoms [19].
esterification. Also, as the length of the formed
ester increases, its odor tends to smell more like
an artificial fruit flavoring [18].

Table 2. Ester formation.

Carboxylic Alcohol Ester Formed Odor Figure 5. Turbidity of Different Alcohol
Acid Derivatives. From left to right, n-butyl alcohol,
sec-butyl alcohol, tert-butyl alcohol.
Formic Ethyl Ethyl formate Rum
Source: Marambio, O.G. (2012, June 5).
Acid alcohol
Alcoholes 2012 test de Lucas. Retrieved from
Acetic Acid Ethyl Ethyl acetate Sweet https://www.youtube.com/watch?v=Ac_e5xe4aP
alcohol odor M&feature=share

Acetic Acid Isopentyl Isopentyl Banana As seen in the image above, the presence of a
alcohol acetate/ isoamyl cloudy formation is only visible in sec-butyl and
acetate tert-butyl. This is because among the three, tert-
butyl undergoes the most stable reaction due to
Acetic Acid Octyl Octyl acetate Orange
the high stability of the intermediate tertiary
carbocation while n-butyl has the most unstable Tert-butyl (CH3)3COH Orange
reaction [20]. alcohol solution

Table 3: Lucas Test Results N- CH3(CH2)2CHO Blue

butyraldehyde solution
CONDENSED
ALCOHOL STRUCTURAL TURBIDITY
Benzaldehyde Blue-green
FORMULA
solution
n-butyl CH3CH2CH2OH no formation of
cloudy formation Acetone CH3COCH3 Orange
solution
sec-butyl CH3CHOHCH2CH3 slow formation of
cloudy formation Acetophenone Orange
solution
tert-butyl (CH3)3COH immediate
cloudy formation

Table 3 indicates the rate of turbidity of n-

butyl, sec-butyl and tert-butyl in Lucas reagent. Table 4 indicates the positive and negative
N-butyl had no visible reaction and the solution results of chromic acid test on various samples,
remained colorless, this indicates a negative specifically, n-butyl alcohol, sec-butyl alcohol,
result. Turbidity was most visible in tert-butyl tert-butyl alcohol, n-butyraldehyde,
with rapid formation of cloudy formation. There is benzaldehyde, acetone, and acetophenone.
also a presence of cloudy formation in sec-butyl,
however, its reaction was much slower compared
to the reaction in tert-butyl. Sec-butyl and tert-
butyl both yielded positive results indicating that
there is a formation of chloroalkane in the
solution [19].

Chromic Acid Test

Chromic acid, H2CrO4, is a strong acid [21].
Because of this, chromic acid is used to detect
the presence of alcohols (specifically, primary
and secondary alcohols). It is also used to
differentiate aldehydes from ketones [22]. A
positive result for this test shows a blue-green
solution due to the oxidation of certain
compounds because of the formation of the ion
Cr+3 [23]. Aldehydes and primary alcohols
undergo oxidation resulting to the formation of
carboxylic acids while oxidizing secondary
alcohols led to the formation of ketones. The ion
Cr+6 found in the chromic acid then undergoes
reduction resulting to the ion Cr+3 [24]. Tertiary
alcohols however, do not undergo oxidation
anymore because of its stable chemical state.
Table 4. Chromic Acid Test Results
Sample Condensed Structural Chromic
Formula Acid Test
N-butyl CH3CH2CH2CH2OH Blue
alcohol solution
Sec-butyl CH3CHOHCH2CH3 Blue
alcohol solution
Figure 4. Chromic Acid Test Results. From left to
right, N-butyl alcohol, sec-butyl alcohol, tert-
butyl alcohol, n-butyraldehyde, benzaldehyde,
acetone, acetophenone.
N-butyl alcohol and sec-butyl alcohol showed
positive results in the chromic acid test since they
both produced a blue solution because they are
primary and secondary alcohols, respectively.
Tert-butyl alcohol however, resulted in an orange
solution which means that it is a negative result
in the chromic acid test since it is a tertiary
alcohol. Both n-butyraldehyde and benzaldehyde
garnered positive results (blue solution) since
both are aldehydes while acetone and
acetophenone produced orange solutions
(negative result) since they are both ketones.
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