Results and discussion

Hydroxyl- and carbonyl-containing compounds were put into tests in order to identify whether
it is primary, secondary or tertiary alcohol and another set of tests to differentiate aldehydes from
ketone.

1. Solubility of alcohols in water

Table 1. Solubility of alcohols in water

Alcohol Amount of water (in Solubility in water
mL) needed to
produce a
homogenous
dispersion
Ethanol 1 mL soluble
n-butyl alcohol 1.5 mL soluble
sec-butyl alcohol 1 mL soluble
tert-butyl alcohol 1 mL soluble
Benzyl alcohol 2 mL insoluble
As seen on the table above, Ethanol, n-butyl alcohol, sec-butyl alcohol and tert-butyl
alcohol were all soluble in water while only benzyl alcohol was insoluble in water. Ethanol, sec-
butyl alcohol and tert-butyl alcohol needed 1 mL of water to be soluble in water and n-butyl
alcohol needed 1.5 mL to be soluble in water.
There are several factors for alcohols to differ in solubility in water. Initially, it follows the
principle of “like dissolves like” which states that polar compounds such as alcohol are soluble
to another polar compound which was water. But not all of the alcohol tested was soluble in
water, this was due to factors such as number of carbon atoms in the compound and branching
of the carbon chains. The number of carbon atoms affect the solubility because water forms
hydrogen bonds with the hydroxyl group and the energy of formation of these hydrogen bonds
is greater than the energy lost from breaking the alcohol-alcohol hydrogen bonds[1]. Ethanol
is the most soluble alcohol compared to butanols due to it having only 2 carbon atoms while
the butanols contain 4 carbon atoms. Alcohols with carbon atoms of 6 and above such as
Benzyl alcohol are insoluble in water due to them having larger nonpolar hydrophobic effect
overcoming the hydrophilic effect of alcohol [1]. Branching of carbon chains affect solubility
due to decreased surface area of molecules because they are more compact when branched.
The intermolecular attractive forces become weak when compact hence they are more soluble
in water [2]. This explains why among the butanols, n-butyl alcohol requires more water in
order to be soluble.
2. Lucas test

Table 2. Results of Lucas test

Test compounds Observation
n-butyl alcohol colorless
sec-butyl alcohol slightly turbid
tert-butyl alcohol turbid
To determine whether each butanol is a primary, secondary or tertiary alcohol, Lucas test was
done. The results of Lucas test was n-butyl alcohol yielded a colorless solution, sec-butyl alcohol
had a slightly turbid solution and lastly, tert-butyl alcohol was turbid and there was a formation of
a cloudy layer. Tert-butyl alcohol had the shortest time to form the layer, followed by sec-butyl
alcohol then the longest time was n-butyl alcohol.
Lucas test is conducted only on alcohols with lower molecular weight and it can’t be test on
alcohols with more than six carbon atom. The Lucas reagent Zinc Chloride acts as catalyst which
enhances the formation of carbocations and difference in reaction with concentrated hydrochloric
acid determines the classification of alcohols, with turbidity due to formation of alkyl chloride as
an indication for positive result [3].

Figure 1. SN1 mechanism of secondary alcohol

Figure 2. SN2 mechanism of primary alcohol

The reaction mechanism involved in the Lucas test is based on SN1 nucleophilic substitution
reaction but only sec-butyl alcohol and tert-butyl alcohol undergo SN1 mechanism because n-butyl
alcohol undergo SN2 mechanism. On SN1 reaction, there is a formation of carbocation as an
intermediate product which is stable due to the charges are equally distributed to the terminal
carbon atoms. The high reactivity of tertiary alcohols such as tert-butyl alcohol is attributed to the
great stability of the carbocation. On the other hand, SN2 doesn’t produce an intermediate
carbocation due to it being too unstable, hence primary alcohols such as n-butyl alcohol is reactive
[3].Overall, the order of reactivity of alcohols are tertiary alcohols being the fastest to react
followed by secondary alcohols, and then the primary alcohols.
3. Chromic acid test

Table 3. Results of chromic acid test

Test compounds Observation
n-butyl alcohol blue-green solution
tert-butyl alcohol orange solution
Acetaldehyde blue-green solution
Benzaldehyde blue-green solution
Acetone orange solution
Acetophenone orange solution
Isopropyl alcohol blue-green solution
Chromic acid test or jones oxidation test is a test for compounds that possess reducing
property. This test was used to differentiate primary alcohol from tertiary alcohol and aldehydes
from ketones. An indication of positive result on chromic acid test is the disappearance of the red-
orange color of chromic acid and turning to a blue-green color, this is due to the presence of the
Chromic (III) ion [4]. According to table 3, n-butyl alcohol, Acetaldehyde, Benzaldehyde and
Isopropyl alcohol yield a positive result of blue-green solution while tert-butyl alcohol, Acetone
and Acetophenone resulted in an orange solution

Figure 3. Reaction of alcohols and aldehyde with chromic acid

Chromic acid test involved reduction-oxidation reactions. Chromic acid is a reagent for
oxidizing primary alcohols and aldehyde to carboxylic acids and secondary alcohols to ketones.
Primary, secondary alcohols and aldehydes were subjected to oxidation while chromium was
subjected to reduction from Cr6+ to Cr3+. They reduced the orange-red chromic acid reagent to a
blue-green suspension of Chromic (III) salts [5]. Hence, Primary, secondary alcohols and aldehydes
give positive results. Tertiary alcohols and ketones doesn’t undergo the reaction because there are
no carbon-hydrogen bonds available to be oxidized [6].
4. 2,4-Dinitrophenylhydrazone (2,4-DNP) test

Table 4. Results of 2,4-Dinitrophenylhydrazone (2,4-DNP) test

Test compounds Observation
Acetaldehyde yellow precipitate
Benzaldehyde orange precipitate
Acetone yellow precipitate
Acetophenone red-orange precipitate
The 2,4-Dinitrophenylhydrazone test was for detection of carbonyl groups in the test
compounds. It gives a positive result on aldehydes and ketones with the formation of yellow or
orange precipitate. As can be seen in table 4, Acetaldehyde and Acetone produced a yellow
precipitate while Benzaldehyde and Acetophenone resulted in orange and red-orange precipitate
respectively.

Figure 4. Reaction of aldehyde or ketone and 2,4-Dinitrophenylhydrazine (2,4-DNPH)

Figure 5. Reaction of benzaldehyde and 2,4-Dinitrophenylhydrazine (2,4-DNPH)

The mechanism for DNP test is condensation or addition and elimination. It involved the
nucleophilic addition of NH2 to the C=O and elimination of H2O. The strong nucleophile in the lone
pair of electrons on the terminal NH2 of 2,4-DNPH attacks the electrophilic carbonyl carbon with
the elimination of H2O which produced 2,4-dinitrophenylhydrazone and is an insoluble solid [7].
The precipitate may be oily at first but becomes a crystalline solid on standing for a few minutes.
The color of 2,4-dinitrophenylhydrazone differed due to the structure of the aldehyde or ketone.
Non-conjugated carbonyl compounds usually form yellow precipitate while conjugated carbonyl
compounds yield orange precipitate. Conjugated carbonyl compounds shifts the absorption
maximum to longer wavelengths thus changing the color from yellow to orange or red-orange [8].
5. Fehling’s test

Table 5. Results of Fehling’s test

Test compounds Observation
Acetaldehyde brick-red precipitate
Benzaldehyde blue solution
Acetone blue solution
Acetophenone blue solution
Fehling’s test was test for differentiating aldehydes and ketones. It gives a positive result on
aldehyde with the formation of brick-red precipitate. On table 5, Only Acetaldehyde produced a
brick-red precipitate while Benzaldehyde, Acetone and Acetophenone yield a blue solution.

Figure 6. Reaction of aldehyde and Fehling’s solution

Fehling’s test involved reduction-oxidation reaction with aldehydes oxidized to carboxylic acid
and Cu2+ was reduced to Cu1+. The copper (I) oxide was precipitated out of the reaction mixture
which resulted in the color brick-red of the mixture [9]. Aromatic aldehyde such as benzaldehyde
lacks alpha hydrogens which can’t be oxidized by the Fehling’s solution; therefore, it resulted to a
blue solution [10].

6. Tollens’ silver mirror test

Table 6. Results of Tollens’ silver mirror test

Test compounds Observation
Acetaldehyde silver mirror
Benzaldehyde light yellow solution w/ globules
Acetone dark-gray solution
Acetophenone turbid gray solution

Figure 7. Reaction of aldehyde with tollen’s reagent

7. Iodoform test
Test compounds Observation
Acetaldehyde orange solution
n-butyraldehyde brown precipitate
Benzaldehyde red precipitate w/ globules
Acetone yellow precipitate
Acetophenone red-orange precipitate
Isopropyl alcohol yellow solution

Figure 8. Reaction of ketone and iodoform test reagent

References
[1]https://chem.libretexts.org/LibreTexts/Purdue/Purdue%3A_Chem_26505%3A_Organic_Chemi
stry_I_(Lipton)/Chapter_4._Intermolecular_Forces_and_Physical_Properties/4.4_Solubility

[2] https://www.askiitians.com/forums/Organic-Chemistry/why-the-solubility-of-alcohols-in-
water-increase-w_152560.htm

[3] http://www.chemistrylearner.com/lucas-reagent.html

[4] http://dept.harpercollege.edu/chemistry/chm/100/dgodambe/thedisk/qual/chromic.htm

[5]
https://chem.libretexts.org/Textbook_Maps/Organic_Chemistry/Supplemental_Modules_(Organi
c_Chemistry)/Alcohols/Reactivity_of_Alcohols/The_Oxidation_of_Alcohols/Oxidation_by_Chromi
c_Acid

[6] https://study.com/academy/lesson/chromic-acid-test-for-aldehydes-alcohols-mechanism.html

[7] https://chemistry.stackexchange.com/questions/18481/why-doesnt-the-bradys-test-2-4-
dnph-work-on-carboxylic-acids

[8] https://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/spectrpy/UV-Vis/spectrum.htm

[9] https://chemdemos.uoregon.edu/demos/Fehling-Test

[10] https://chemistry.stackexchange.com/questions/44872/why-does-benzaldehyde-not-
respond-to-fehlings-test