OBJECTIVES

1. To illustrate the oxidation of a secondary alcohol to a ketone which is borneol to

camphor.
2. To characterise and figure out the information about the structure and purity of the
isolated product from its melting point, thin-layer chromatography, infrared
spectroscopy and optical rotation measurements.

INTRODUCTION

Camphor is an isoprenoid and derived from two unit isoprene which consists of five-
carbon atoms. Therefore, it has formula of C10H16O. It also can be produced by the reaction of
oxidation of borneol which is the common method to form camphor. The hydrolysis of the
isobornyl acetate leads to borneol that can be oxidized to form racemic camphor.

Oxidation and reduction reactions or redox reaction is one of most important reaction
which involved reducing agent and oxidising agent. In this experiment, in order to prepare
camphor, redox reactions is involved. The secondary alcohol presence in borneol undergo
redox reaction to produce the ketone that presence in camphor. Camphor is a naturally
compound that can be easily isolated from a certain evergreen tree.

HOCl

HOAc

Figure 1.0

Figure 1.0 shows the oxidation reaction of berneol to camphor.

This experiment illustrates the oxidation of secondary alcohol to a ketone which is

borneol to camphor by using sodium hypochlorite (bleach) in acetic acid which acts as an
oxidant. Due to the acidic environment, hypochlorous acid is likely to act as actual oxidizing
agent which can be obtained from the reaction of hypochlorite and acetic acid. The formula of
the reaction can be generated as below:
 NaOCl + CH3COOH HOCI + CH3COONa

The crude camphor is then purified by sublimation process. The product is

characterized using infrared spectroscopy, thin-layer chromatography, optical rotation
measurement and melting point to figure out the information about the structure and purity.

MATERIALS AND APPARATUS

Table 1.0 shows the lists of materials and apparatus used throughout the experiment.

Materials Apparatus
Bornoel Erlenmeyer flask
Glacial acetic acid Separatory funnel
Clorox Measuring cylinder
Diethyl ether Heat lamp
Sodium bisulfite Aluminium foil
Starch iodine paper Sublimation apparatus
Sodium bicarbonate solution Beaker
Anhydrous Na2SO4
Ice
Table 1.0

PROCEDURE

A. Preparation of (-)-Camphor
1. 500 mg of (-)-borneol was dissolved in 1.5 ml of glacial acetic acid in 25 ml Erlenmeyer
flask and swirled.
2. 4.0 ml of fresh household bleach solution, Clorox which is ca. 5.25% NaOCl in one
batch and swirled.
3. The mixture was swirled occasionally over the 15 min.
4. The sample was tested after 10 minutes with starch iodine paper by placing one drop of
sample on wet-starch iodine paper. Blue colour formed indicate of excess hypochlorite.
5. If the test is negative, a small amount of additional hypochlorite solution is added then
swirl.
6. The reaction mixture was diluted with about 15 ml of water then transferred into 60 ml
separatory funnel with 15 ml of diethyl ether.
7. 0.5 ml to 1.0 ml of saturated sodium bisulfate solution was added in order to reduce any
residual of hypochlorite.
8. The mixture was shaken for at least 20-25 sec before the lower layer being drained.
9. The ether layer was washed with about 8 ml saturated sodium bicarbonate solution.
10. The lower aqueous layer was then drained off and transferred the ether to a small
Erlenmeyer flask.
11. Small amount of anhydrous NaSO4 was added to dry the ether.
12. The solution was decant into a tared 25-ml Erlenmeyer flask and evaporated carefully.
13. The heat lamp was used to warm the flask to room temperature.
14. A portion of the product which about 1-2 mg was kept for melting point and second
portion for determination of IR spectrum.
15. The remaining portion was weighed and sublimed in an sublimation apparatus.
16. The central test tube in the apparatus was filled with ice to ensure the apparatus in cold
condition but the condensation of moisture from atmosphere should be avoided.
17. The camphor was heated from the bottom by using the heat lamp and aluminium foil
was used to shield and cover all except the bottom of the sublimator from the heat.
18. The yield and melting point of the sublimed product was determined.

B. Infrared Spectrum
1. The IR spectrum of the crude and purified was taken by using FTIR spectroscopy.

C. Thin-Layer Chromatography

1. A TLC comparison of samples authentic borneol, authentic camphor and purified

camphor with methylene chloride as developing solvent by using silica gel-plates.
2. The samples were prepared as concentrated solutions in a small amounts of methylene
chloride in three labelled vials.
 D . Optical Rotation

1. 125-150 mg of purified camphor was weighed into a tared 5-ml volumetric flask and
filled with ethanol to the mark.
2. The solution was mixed by inverting the flask with the stopper in place.
3. A 1-dm polarimeter tube was filled and used to obtain a measured rotation sodium-D
line (589 nm).
4. Specific rotation was calculated and compares to the literature value for optically pure
(-)-camphor of -43.8° in ethanol.

DATA AND RESULTS

A: Preparation of (-)-Champor

Observation
Table 2.0 shows the observation of sample tested with iodine paper
Test Observation
Test of sample with iodine paper The iodine paper turns to blue colour
Table 2.0

Table 3.0 shows the mass of crude yield and sublimed yield of camphor.
Type of Mass Mass (g)

Mass of Erlenmeyer flask 18.1319

Mass of Erlenmeyer flask + crude yield 18.3833
Mass of crude yield (impure camphor) 0.2514
Mass of crude yield used for sublimation 0.1036
Mass of sublimation chamber apparatus 78.3627
Mass of sublimation chamber apparatus + sublimed 78.4567
yield
Mass of sublimed yield (pure camphor) 0.0949
Table 3.0
Table 4.0 shows the percentage yield calculated for crude and pure camphor.
Type of Product Percentage Yield (%)

Crude camphor 50.52

Pure camphor 91.60
Table 4.0

Calculation of Percentage Yield for Crude Camphor

 In this experiment, 1 mol borneol as a reactant produce 1 mol of camphor

product.
 Mass of borneol used as reactant : 0.5042 g
 Theoretical yield of crude product produced can be calculated as:

1 𝑚𝑜𝑙 𝑏𝑜𝑟𝑛𝑒𝑜𝑙 152.24 𝑔/𝑚𝑜𝑙

0.5042 g × ×
154.25 𝑔/𝑚𝑜𝑙 1 𝑚𝑜𝑙 𝑐𝑎𝑚𝑝ℎ𝑜𝑟

= 0.4976

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑐𝑟𝑢𝑑𝑒 𝑐𝑎𝑚𝑝ℎ𝑜𝑟

 Formula of percentage yield (crude) = × 100%
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑚𝑎𝑠𝑠
0.2514 𝑔
= × 100%
0.4976 𝑔

= 50.52%
Calculation of Percentage Yield for Pure Camphor

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝𝑢𝑟𝑒 𝑐𝑎𝑚𝑝ℎ𝑜𝑟

 Formula of percentage yield (pure) = × 100%
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑖𝑚𝑝𝑢𝑟𝑒 𝑐𝑎𝑚𝑝ℎ𝑜𝑟

0.09490
= × 100%
0.1036

= 91.60 %

Melting Point
Table 5.0 shows the melting point of the sample
Sample Initial Temperature (start Final Temperature (End
to Melt) °C Melt) °C
Crude 164.3 158.0
Pure 204.5 194.4
Table 5.0

Theoretical camphor: 177 o C – 178 o C

B: IR Spectrum

Table 6.0 shows the peaks of IR spectrum for crude camphor and pure camphor.
Sample Peak (cm-1 )
Crude camphor 1746.27
Pure camphor 1746.66
Table 6.0
C: Thin- Layer Chromatography

Table 7.0 shows the value obtained from Thin-Layer Chromatography

Sample Distance Travel by Distance Travel by Retention Factor,
Solvent (cm) Solution (cm) Rf
Authentic Borneol 8.2000 6.0000 0.7317

Crude Camphor 8.2000 5.9000 0.7195

Purified Camphor 8.2000 7.1000 0.8659

Table 7.0

Calculation for Retention Factor, Rf

 Formula Retention factor (Rf):

Distance travel by solution,(cm)

Rf = Distance travel by solvent,(cm)

 Calculation of retention factor, Rf for authentic borneol.

6.0000 𝑐𝑚
Rf =
8.2000 𝑐𝑚
= 0.7313

 The calculation of retention factor, Rf for authentic camphor and purified

camphor were calculated by using the same formula.
 Figure 2.0

Figure 2.0 shows the TLC plate used during the experiment.

C. Optical Rotation

Table 8.0 shows data for optical rotation.

Mass of Sample Used 0.03 g

Optical Density 0.5
Angular Rotation -0.09 anc
Theoretical Specific Rotation -43.8 °
Experimental Specific Rotation -30.0 °
Table 8.0
Calculation for Specific Rotation

 The mass used is 0.03 g and the volume used is 10 ml, hence the the
concentration of solution is 0.003 g/ml.
 Formula of Specific Rotation :

𝛼
[α] =
𝑐 ×𝑙

(−0.09°)
= (0.003 𝑔/𝑚𝑙)(1𝑑𝑚)

= -30.0 °

 Where [α]= the specific rotation

α = the observed rotation

c = the concentration of solution in grams per millilitre (g/ml)

l = the length of the cell in decimetres (dm)

Calculation for percentage error:

[ 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑣𝑎𝑙𝑢𝑒−𝑎𝑐𝑡𝑢𝑎𝑙 𝑣𝑎𝑙𝑢𝑒]

Percentage error = × 100%
[𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑣𝑎𝑙𝑢𝑒]

[43.8−30]
= × 100%
[43.8]

= 31. 51%
 DISCUSSION

A. Preparation of (-)-Camphor

In this experiment, borneol which is secondary alcohol undergoes oxidation reaction

to form camphor which is ketone. When hypochlorous acid was added, the hydroxyl group that
attached to the carbon is replaced by the OCl- formed. Therefore, oxidation process occurred
as the other H atom that attached at the same carbon accept the electron from H2O molecules
and become H3O+. H3O+ can leave the compound easily as it is a good leaving group. This is
can be accomplished due to the breaking bond between C and H3O+ by donating the electron
to the O atom. Alkyl hypochlorite intermediate is produced, which then proceed via an E2
elimination. Hence, Cl group that attached to the oxygen atom departed as it acts as a leaving
group. The mechanism process can be illustrated as below:

Figure 2.0

Figure 2.0 shows the mechanism of the oxidation borneol to camphor.

Bleach solution which was Clorox that contained ca.5.25% NaOCl is used to oxidise the
borneol. Hence, it acts as an oxidizing agent which will form a good oxidizing agent of
hypochlorite ion ClO-. This makes the hypochlorite ion release oxygen and leave Cl- . As
mentioned, hypochlorous acid was produced as acetic acids was added to the glacial which will
provide acidic environment. It is likely that the actual oxidizing agent is hypochlorous acid,
HOC1. The mixture was then tested with starch-iodine paper to ensure the hypochlorite
oxidizing agent was in excess so that the reaction could go to completion. The starch-iodine
paper turns to blue colour because of the presence iodine. This is because iodide ions oxidized
by hypochlorite ions to iodine.
 The experiment was proceed with extraction process by using separatory funnel. Two layer
was formed which consists of ether layer at upper and aqueous layer at the bottom. The ether
layer is washed with about 8 ml of saturated sodium bicarbonate solution. Sodium bicarbonate
is used in order to neutralize and remove unreacted compound which is acidic in ether solution.
The aqueous layer was drained off while the ether was then dried with small amount of
anhydrous Na2SO4. The solution was decant and heat lamp was used to evaporate the ether.
Before purification process was done, a few portions of crude camphor was kept for melting
point, thin-layer chromatography, IR spectrum and optical rotation. The percentage yield for
crude camphor produced is 50.52%.

The remaining product was proceed with sublimation process to purify it. The sublimation
process was carried out by using sublimation apparatus which the central test tube was added
with ice water to make sure the apparatus in cold condition. After 30 minutes, the purified
camphor surround the outer central test tube with a white, crystalline solid appearance. The
mass of the pure camphor was taken and the percentage yield calculated is 91.60%. A few
portions of camphor also was used for melting point, thin-layer chromatography, IR spectrum
and optical rotation.

The both products which is crude and pure was analysed by taking their melting points.
For crude camphor, it started to melt at 163.0°C and completely melt at 204.5°C while pure
camphor started to melt at 158.0°C and completely melt at 194.4°C. Based on their melting
points, we can justify the purity of the camphor produced. This can be seen that the melting
points of crude is higher than the pure. This is because of some impurities presence in crude
that causes the crude required high temperature to melt compared to pure. Therefore, pure
camphor is more purified than crude as it undergo sublimation process. Theoretically, the pure
and dry camphor will completely melts at 177°C – 178 °C. In this experiment, our pure
camphor completely melts at 194.4°C due to some errors.

B. IR spectrum

In order to verify the oxidation was successful or not, this can be done by determining
the infrared spectrum of camphor product. The infrared spectrum was done by using FTIR
spectroscopy. By referring to infrared spectroscopy correlation table, the peak for carbonyl of
cyclic 5-membered ketone is 1750 cm-1 . Based on IR spectrum 2.0, the IR spectrum of pure
camphor has peak 1746.66 cm-1 indicates the presence of carbonyl which is cyclic 5-membered
ketone in pure camphor. Camphor is made up of two unit isoprene of cyclic 5-membered. The
peaks in the IR spectrum of our pure camphor do not depict the peak value for alcohols or
phenols which is in range of 3610-3670 cm-1 and 3200-3400 cm-1 . Therefore, the IR spectrum
of pure camphor proves that had no trace of O-H bond which concludes that hydroxyl group
or alcohol was absent in the pure camphor. It was also as an evident that the borneol was
successfully oxidise into camphor as a product due to the presence of the C=O double bonds
which is carbonyl.

The comparison between crude’s IR spectrum and pure camphor’s IR spectrum has been
made to justify the purity of pure camphor. Based on IR spectrum of crude, the C=O double
bonds of carbonyl is presence in crude because the peak is 1746.27 cm-1 . Therefore, the borneol
is oxidise to camphor. But, FTIR detects the O-H bonds from hydroxyl groups which presence
in crude as the peak’s wavelength is 3340 cm-1 and the peak’s appearance is broad. This can be
said O-H bonds presence due to impurities in crude compounds because it does not undergo
sublimation. Therefore, sublimed camphor has higher purity than crude camphor.

C. Thin-Layer Chromatography

The reaction was then followed by thin-layer chromatography in order to monitor the
oxidation. TLC is very useful as it analyses the polarity of each compound and helps in
separating non-volatile components of a mixture by referring their retention factor, Rf. In this
experiment, authentic borneol, crude camphor and purified camphor were monitored by TLC
plate. Silica gel is used as polar stationary phase. The mobile phase used is methylene chloride
which is non-polar solvent. Methylene chloride has slightly polarity compared to water hence
we refer methylene chloride as non-polar. Moreover, the most important feature methylene
chloride is lack in ability to form hydrogen bonds, which makes mixing with water very
unfavourable and miscible in certain organic solvents. Therefore, we refer methylene chloride
in this experiment as non-polar solvent. In other words, when the stationary phase is polar and
the mobile phase is non-polar, the method is normal-phase.

Based on the Table 7.0, the highest Rf. is purified camphor which is 0.8659. Purified
camphor travel furthest compared to crude camphor and authentic borneol. This is because
purified camphor has least polarity due to the ketone in the molecule. Purified camphor unable
to form hydrogen bond with the silica gel due to its non-polar properties. Thus, purified
camphor interact less with the polar silica gel which leads to rapid movement past the stationary
phase.

The lowest Rf value is 0.7195 which is crude camphor. Theoretically, Rf value for crude
camphor must be higher than authentic borneol but due to some errors the results were opposite.
Rf value for crude camphor supposedly to be higher because crude camphor is non-polar
compared to authentic borneol and supposed to travel more because it form less interaction
with polar silica gel. Authentic borneol is polar because it contains hydroxyl group as it is
secondary alcohol. Therefore, it should interact with the silica gel by forming hydrogen bonds
as both are non-polar so authentic borneol will travel less compared to crude camphor.

D. Optical Rotation

Optical activity is the ability of a chiral compound to rotate plane polarized light. All
enantiomers exists as chiral compound. Therefore, camphor is enantiomer which had the ability
to rotate the plane polarized light. The rotation of plane polarized can occur either in
anticlockwise or clockwise rotation. The enantiomer is categorized as loverotatory if the
direction of the plane-polarized light was left or anticlockwise. Unlike loverotatory,
dextrorotatory is when the enantiomers can rotate the plane-polarized light in opposite direction
which is right or clockwise. (R) and (S) configuration are not affecting the direction of the
rotation plane-polarized light. Thus, we could determine whether the purified camphor
produced is loverotatory which is (-) or dextrotatory which is (+).

In this part, we measured the optical rotation of purified camphor which the specific
rotation [α] can be determined. The specific rotation of a chemical compound [α] is defined as
the observed angle of optical rotation α when plane-polarized light is passed through a sample
with a path length of 1 decimeter and a sample concentration of 1 gram per 1 milliliter. 0.03 g
of purified camphor is used in 10 ml ethanol. Therefore, the concentration obtained is 0.003 g
ml-1. Therefore, the specific rotation for our purified camphor calculated is -30°. Theoretically,
the specific rotation for pure (-)- camphor is -43.8°. The percentage error of this optical rotation
is 31.51%. The specific rotation obtained is negative, therefore purified camphor is said to be
leverotatory. So (-)-camphor can rotate the plane-polarized light in anticlockwise direction.
 There are some errors in this experiment that leads to inaccuracy of results. Firstly, the
melting points of our pure camphor is not in range for theoretical melting point as it completely
melts at 194.4°C but the theoretical range is at 177°C – 178 °C. This is because the pure
camphor put in capillary tube is too large which resulting in a melting point range is too wide
and possibly high. Moreover, the heating rate was set faster than five degrees per minute which
lead to inaccuracy of reading in melting point. Next, the retention factor,Rf value obtained for
crude camphor is lower than Rf value of authentic borneol. The results supposed to be the Rf
value of crude camphor is higher than Rf value of authentic borneol. This is because the
concentration of the crude camphor is too diluted that causes the crude camphor travel less
compared to authentic borneol.

The precaution steps are when the sodium bicarbonate is used during the extraction, the
separatory funnel must be vented immediately as it produces high pressure that can cause an
explosion. Next, the evaporation process by using heating lamp must be covered with
aluminium foil to enhance the evaporation process. Lastly, during thin layer-chromatography,
the sample must be pipetted immediately on the TLC plate as it is volatile.

QUESTIONS

1. Write a balanced equation for the oxidation of (-)-borneol to (-)-camphor with

HOCl (hypochlorite in acid) going to HCl.

Balance equation : C10H18O (s) + HOCl (l) → C10H16O (s) + HCl (l) + H2O (l)
2. Borneol can also be oxidised to camphor with other oxidising agent, such as
sodium dichloromate in acid. Write a balanced equation for this oxidation (
Cr2O7 2- is reduced to Cr3+). What the weight of Na2Cr2O7. 2H2O should be
needed (theoretically) to oxidise 0.50 g of borneol?

Balanced equation:
3C10H18O (s) + Na2Cr2O7 (s) + 4H2SO4 (l) → 3C10H16O (s) + 7H2O (l) + Na2SO4 (l) +
Cr2 (SO4)3

The weight of Na2Cr2O7. 2H2O should be needed (theoretically) to oxidise 0.50 g of

borneol can be calculated as shown below:

Borneol = C10H18O
Mass of borneol = 0.5 g
Molar mass of borneol = 10(12.01) + 18(1.008) + 16
=154.24 g/mol =

No of mole of C10H18O
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑏𝑜𝑟𝑛𝑒𝑜𝑙
=
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑏𝑜𝑟𝑛𝑒𝑜𝑙
0.5 𝑔
=
154.24 𝑔/𝑚𝑜𝑙

= 0.0032 mol

 1 mole borneol required 1 mole of Na2Cr2O7. 2H2O to be oxidised.

Hence 0.0032 mol C10H18O = 0.0032 mol Na2Cr2O7. 2H2O

Molar mass of Sodium dichloromate:

= 2(22.99) + 2(51.99) + 7(16) + 4(1.008) + 2(16)
= 298 g/mol
 Mass of Sodium dichloromate obtained:
= 0.0032 mol x 298 g/mol
= 0.954 g

3. What portion of the spectrum will not be useful because methylene chloride was
used as the solvent?

1400 cm-1 to 400 cm-1

4. What conclusions can be drawn about the presence or absence of unreacted

starting material?

The reaction of the material depends on the rate of reaction and temperature of the
system pressure.

5. Which compound (-)-borneol or (-)-camphor, has the highest vapor pressure?

(-)-Camphor has the highest vapor pressure.

CONCLUSION

In conclusion, the secondary alcohol which is borneol undergo oxidation to form ketone
which is camphor. The percentage yield of crude camphor obtained from this experiment is
50.52% while the percentage yield for pure camphor is 91.60%. The purity of the camphor is
then monitored by melting point, thin-layer chromatography, IR spectroscopy and optical
rotation. The melting point obtained for crude camphor is from 164.3 to 204.5°C while pure
camphor is 158.0-194.4 °C. The Rf value calculated for authentic borneol, crude camphor and
pure camphor are 0.7317, 0.7195 and 0.8659 respectively. The IR spectrum of absorption peak
depicted from both crude camphor and pure camphor are 1746.27 cm-1 and 1746.66 cm-1
respectively. Thus, the C=O carbonyl of ketone is presence in both crude and pure as the
borneol undergo oxidation reaction to form ketone. Lastly, the specific optical rotation for pure
camphor was calculated which is -30° with the percentage error 31.51%. The specific rotation
obtained is negative, therefore purified camphor is said to be leverotatory. So (-)-camphor can
rotate the plane-polarized light in anticlockwise direction.