Experiment 3: OXIDATION-REDUCTION IN ORGANIC CHEMISTRY

CHM 303 Section B07 (Wed. 7:30-10:20 PM)

Mideum Abraham Park
Xin Teng
Completed: 10/28/15
Reported: 11/22/15

Purpose:
To perform an oxidation-reduction Cannizzaro reaction on an aldehyde and obtain the
products for analysis.
Procedure:
(Refer to OPB(14)-pp 23-29 for the full procedure.)
Data:
Aldehyde # 145
Weight of the acid collected: 109 mg
Weight of alcohol collected: 482 mg
IR of alcohol attached
Table of Peaks in 4000-500 cm-1:
Obtained IR

47.7

Character
(w, m, s,
br)
m, br

2885.95
1502.87

51.5
13.4

m
m

1490.22

10.9

m,

1444.79
1250.45
1095.95
1039.50
927.55
803.83
768.19
736.91
702.64

12.1
6.2
41.3
9.6
35.0
33.8
49.8
32.0
56.6

Wavenumber
(cm-1)
3359.85

Intensit
y

Authentic IR
Wavenumber
(cm-1)

Intensit
y

Melting point of the carboxylic acid:

Raw Sample: 231-233 C

Anthracene: 216-218 C

Corrected: 230-232 C (-1.0 C from original)

Character Representation
(w, m, s,
br)
O-H stretch w/
H-bonds
C-H stretches
Aromatic C==C
stretches
Aromatic C==C
stretches

Report Questions:
1. Whenever you make a new solid product, it is essential to describe the crystals. The
following terms are recognized ways to do this:
1) needles (long, one dimension much larger than the other two)
2) plates (flat, two dimensions much longer than the other one)
3) compact, cubic (all three dimensions the same, like rock salt)
4) compact, lozenge (not cubic or triangular, but all three dimensions about the same)
5) compact, prismatic (triangular, all three dimensions about the same)
6) dendritic (feathery, very branched, like snowflakes)
7) granular (crystals too small to have visible shape, like table sugar)
8) microcrystalline (a powder)
Describe the crystals of your recrystallized carboxylic acid. (Remember to include their
color.)
The crystal was granular and white.

2.

Summarize all possible unknowns. If you can pin the answer down to one un- known,
good. If not, go as far as possible.
According to the melting point analysis, the carboxylic acid in question is most nearly
either diphenic or 4-chlorobenzoic acid, which both has melting points of 229 C. But
since diphenic acid is a diprotic acid, the O-H stretch peak on of its IR spectra may be
significantly broader than shown in the collected data (due to variance in H-bonding).
Therefore, the starting compound is 4-chlorobenzaldehyde.

Looking at 11 C below and above the obtained melting point, we have four options:
NAME

MP (C)

3-Hydroxy-2-naphthoic

223 C

1-Hydroxy-2-naphthoic

226 C

Diphenic

229 C

3,4-Methylenedioxybenzoic (Piperonylic)

229 C

3.

Why does any unreacted aldehyde end up contaminating the alcohol fraction and not the
carboxylic acid fraction? At what stage is the carboxylic acid formed from its anion?
When the Cannizzaro reaction occurs, it forms alkoxide ion and acid anion. But since
alkoxide has tendency to grab hydrogen better than hydroxide, it grabs a hydrogen from
the solvent, H2O, to form an alcohol.
Since carboxylic acid is still in its anion form, it stays in water fraction, while the
untreated aldehyde and neutralized alcohol enters the DCM layer. When the layers are
separated, DCM layer contains the unreacted aldehyde alongside the alcohol.

Carboxylic acid is formed from its anion when the acid is added to H+ ions to the anion.
This is difference is that alkoxide anion of the alcohol in that alkoxide is able to grab H+
ions from the solvent, H2O.

4.

The yields of the product carboxylic acid and alcohol can be computed from the volume
of starting material. If 0.80 mL of 3-methylbenzaldehyde (m-tolualdehyde) (density =
1.019 g/mL) were used, what is the percent yield if 0.44 g of 3-methylbenzoic acid (mtoluic acid) were produced? What is the percent yield if 0.38 g of 3-methyl- benzyl
alcohol were produced? [Hint: Pay attention to the stoichiometry of the Cannizzaro
reaction! Remember two moles of aldehyde gives one mole of carboxylic acid and one
mole of alcohol.]

mcarboxylic acid=0.80 mL

g 1 mol aldehyde
1 mol acid
136.15 g
=0.46 g
( 1.019
)(
)(
)(
mL
120.15 g
2mol aldehyde 1mol acid )

yield of carboxylic acid=

malcohol=0.80 mL

0.44 g
=96 yield
0.46 g

g 1 mol aldehyde 1 mol alcohol

122.16 g
=0.41 g
( 1.019
)(
)(
)(
mL
120.15 g
2mol aldehyde 1 mol alcohol )

yield of alcohol=

0.38 g
=93 yield
0.41 g