Marjory Joy R.

Castillo Locker 5C
Experiment #8: Auto-Oxidation-Reduction of Benzaldehyde November 13, 2019

I. Data and Results

Table 1. A comparison among the characteristics and qualitative test results of benzaldehyde, benzyl alcohol, and benzoic
acid obtained from the experiment

Benzaldehyde Benzyl Alcohol Benzoic Acid

Appearance Yellow-orange Clear, yellow White, powdery
liquid liquid crystals, slightly
shiny
Theoretical Yield N/A 2.70 g 3.05 g
Percent Yield N/A 203.3% 26.6 %
Solubility in Not tested Not tested +
Qualitative 5% NaHCO3
Tests 2,4-DNPH + - -
Tollen’s Test + - -

150
100
50
0
4000 3500 3000 2500 2000 1500 1000 500 0
Wavenumber (cm-1)

Figure 1. Literature IR spectrum of benzoic acid

Figure 2. IR spectrum of benzoic acid obtained from the experiment

Figure 3. Literature IR spectrum of benzyl alcohol

 80
60
40
20
0
4000 3500 3000 2500 2000 1500 1000 500 0
Wavenumber (cm-1)

Figure 4. IR spectrum of benzyl alcohol obtained from the experiment

II. Discussion

Benzaldehyde is an aromatic aldehyde consisting of a benzene ring with a formyl

substituent and it is widely used in the preparation of dyes, perfumes and flavoring agents. (1)
In the process called disproportionation, benzaldehyde acts as both a reducing and an
oxidizing agent when reacted with a strong base like sodium hydroxide (NaOH) to produce
benzyl alcohol and sodium benzoate respectively. Discovered by Stanislao Cannizzaro, the
Cannizzaro reaction explains the nucleophilic addition of the hydroxide ion (OH-) to the
aldehyde which yields a tetrahedral intermediate. When the hydride ion leaves, the
intermediate is oxidized to produce sodium benzoate which will be reacted with hydrochloric
acid (HCl) to yield benzoic acid. Meanwhile, some of the remaining alkoxide ion will react
with water to regenerate the -OH ion that will lead to the formation of benzyl alcohol through
reduction. (2) (Figure 5)

Figure 5. Cannizzaro reaction mechanism

Formaldehyde undergoes a Cannizzaro reaction like benzaldehyde. However, if

formaldehyde and benzaldehyde are treated at the same time with NaOH, a Crossed
Cannizzaro reaction will take place. By having a more positive carbon in its carbonyl group,
formaldehyde will be favored by the nucleophilic attack of NaOH and will be oxidized to
formic acid. On the other hand, a hydride ion will shift from the formate ion intermediate to
the benzaldehyde molecule and an acid-base reaction will take place to reduce benzaldehyde
and form benzyl alcohol. (3) [AtQ 3] (Figure 6)

H H

H
H
This experiment aimed to determine the percent yield of benzyl alcohol and benzoic
acid through the auto-oxidation-reduction of benzaldehyde by reacting it with NaOH. The
products will then be confirmed through
Figure 6. Crossed qualitative
Cannizzaro tests
reaction of and IR spectroscopy.
formaldehyde and
benzaldehyde
The percent yield for benzoic acid and benzyl alcohol were determined to be 26.6%
and 203.3% respectively. For benzoic acid, the factors that decreased the yield include
spillage and product loss during sample transfer and the failure to produce good crystals as
the solution precipitated because the recrystallization was done abruptly. A higher yield of
benzoic acid can be expected if the procedure was followed carefully. The reaction mixture
should be agitated by shaking it vigorously because the first step in Cannizzaro reaction is
reversible. (2) (Figure 5) Furthermore, enough time should be given for benzaldehyde to react
with NaOH completely. If a similar experiment was conducted without shaking the reaction
mixture properly and without leaving it for 15 minutes before the addition of HCl, benzoic
acid will not precipitate. Benzaldehyde oxidizes during the 15-minute interval to form
sodium benzoate which will then react with HCl to form benzoic acid. Without sodium
benzoate, benzoic acid will not be produced no matter how much HCl is added to the reaction
mixture. (4) [AtQ2]
As for the benzyl alcohol, more than 100% yield was obtained because hexane was
not completely distilled from the organic layer. The time may have been inadequate or the
temperature during distillation may have been lower than the boiling point of hexane. The
purpose of washing the starting solution with hexane was to separate and extract the benzyl
alcohol from the organic layer. [AtQ 1] Benzyl alcohol is soluble with hexane, but hexane is
insoluble with water hence only benzyl alcohol will get into the organic layer.
To detect the presence of carboxylic acid in the crystals obtained, the test for
solubility in 5% sodium bicarbonate was employed. The positive result indicates that the
product has benzoic acid. The crystals were also subjected to IR spectroscopy for further
confirmation. Although the medium C-O stretch at 1710 cm -1 found in the literature IR
spectrum (Figure 1) is only slightly recognizable in the IR spectrum of the product (Figure 2),
the major indication that confirms the identity of benzoic acid is the strong broad O-H stretch
at 2500-3100 cm-1 found in both spectra. Meanwhile, 2,4-DNPH and Tollen’s Test resulted
negative for benzyl alcohol which meant that benzaldehyde was completely removed. The
presence or absence of alcohol was not tested because Chromic acid test also tests positive
for benzaldehyde thus may give a misleading result. Benzyl alcohol was further characterized
through IR spectroscopy and the strong broad tongue present at 3400-3650 cm -1 in the
literature spectrum (Figure 3) was almost invisible in the IR spectrum of the product (Figure
4). This indicates that there is only a weak OH signal in the product. But since an alcohol C-
O stretch is visible at 1050-1150 cm-1 in both spectra, the presence of benzyl alcohol in the
solution can be confirmed.
Benzoic acid and benzyl alcohol were successfully produced by reacting
benzaldehyde with NaOH. To improve the yield of benzoic acid, sample loss should be
minimized by using bigger glassware like a beaker for harvesting and weighing the crystals.
Recrystallization should also be given more time to be able to produce good crystals rather
than precipitates. For benzyl alcohol, the product can be improved by employing the liquid-
liquid extraction with more hexane washes and by distilling all the hexane from the solution.

III. Sample Calculation

A. Theoretical Yield

a. Benzyl Alcohol
g
108.14 benzyl alcohol
1 mol
5.3 g benzaldehyde × × =2.70 g benzyl alcohol
2 g
106.12 benzaldehyde
mol
b. Benzoic Acid
g
122.12 benzoic acid
1 mol
5.3 g benzaldehyde × × =3.05 g benzoic acid
2 g
106.12 benzaldehyde
mol
B. Percent Yield

a. Benzyl Alcohol
actual yield
¿ × 100
theoretical yield
5.49 g
¿ ×100
2.70 g
¿ 203.3 %

b. Benzoic Acid
actual yield
¿ × 100
theoretical yield

0.81 g
¿ ×100
3.05 g
 ¿ 26.6 %

IV. References

1) Brown WH. Benzaldehyde [Internet]. Encyclopædia Britannica. Encyclopædia

Britannica, inc.; 2011 [cited 2019Nov18]. Available from:
https://www.britannica.com/science/benzaldehyde
2) Guidote, A., del Rosario, D., Abuzo, A., Experiencing organic chemistry. Office of
Research and Publication. Ateneo de Manila Univeristy. Quezon City.
(Comprehensive). 2019 Edition. Palardonio, S., & Mostrales, D.C.
3) Benzoic Acid [Internet]. Benzoic Acid - an overview. ScienceDirect; [cited
2019Nov18]. Available from: https://www.sciencedirect.com/topics/agricultural-and-
biological-sciences/benzoic-acid
4) IR Spectra of Selected Compounds [Internet]. Chemistry LibreTexts. Libretexts; 2019
[cited 2019Nov18]. Available from:
https://chem.libretexts.org/Ancillary_Materials/Laboratory_Experiments/Wet_Lab_E
xperiments/Organic_Chemistry_Labs/Misc/IR_Spectra_of_Selected_Compounds
5) Gurupakash Academy. Cross Cannizzaro Reaction [Internet]. Youtube. 2013 [cited
2019Nov16]. Available from: https://www.youtube.com/watch?v=a0e6Pq64yMY