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EXPERIMENT #1

THE PREPARATION OF CYCLOHEXANONE FROM CYCLOHEXANOL

Abstract

This lab experiment proposes the Oxidation of an alcohol by reacting cyclohexanol with

dichromate and concentrated hydrochloric acid. Useful methods for preparation of ketones

include the coupling of acid chlorides with organ copper- reagents and the hydration of

alkynes. Aldehydes can be prepared by reduction of acid chlorides with certain metal

hydrides or by catalytic hydrogenation. However, the most important and commonly used

method for preparation of both ketones and aldehydes is the oxidation of alcohols. Alcohols

are among the most readily available organic compounds, and therefore, this method for

preparation of ketones is extremely useful in this experiment. Primary and secondary

alcohols are oxidized to corresponding ketones by various oxidizing agents and the ketones

derived from secondary alcohols are stable to further oxidation. Thus, in this experiment

cyclohexanol was converted successfully to 3.61g of cyclohexanone and the percentage

yield was calculated as 38.37% but sometimes the results cannot be accurate always due to

some errors have encountered while dealing with measurement and other processes in this

experiment.

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Aims

The main aim of this experiment was to perform an oxidation reaction involving the inter-conversion
of cyclohexanol to form cyclohexanone using Cr2O7-2 as reactant agent.

Apparatus

In order to come with accurate results, there must be fully equipped with apparatus or equipment in
an experiment room. Therefore, the following are some equipment were accurately used in this
practical: Test tubes, conical flask, 100mL beaker, Erlenmeyer flask, Bunsen burner, distillation
apparatus and chemical solutions (11g Concentrated sulphuric acid, 6g Cyclohexanol solution, 12.5g
sodium dichromate dihydrate and aluminium carbonate magnesium sulphate and sodium chloride ),
distilled water and separatory funnel.

Introduction

Oxidation-reduction reactions play an important role in organic chemistry. Oxidation of alcohols to

form aldehydes, ketones or carboxylic acids is a fundamental and widely used reaction. Primary
alcohols can be oxidized to aldehydes or carboxylic acids while secondary alcohols oxidize to
ketones. They are common in nature and are often key intermediates in organic synthesis.
Aldehydes can be prepared by reduction of acid chlorides with certain metal hydrides or by catalytic
hydrogenation. However, the most important and commonly used method for preparation of both
ketones and aldehydes is the oxidation of alcohols. Alcohols are among the most readily available
organic compounds, and therefore, this method for preparation of aldehydes and ketones is
extremely useful in this experiment. (Practical Manuel, Mr. Belly Asong 2020)

Primary and secondary alcohols are oxidized to corresponding aldehydes and ketones by various
oxidizing agents, e.g., dichromates, t-butyl hypochlorite, hypochlorous acid, potassium
permanganate, and nitric acid. The aldehydes derived from primary alcohols can be further oxidized
to carboxylic acids by some of these oxidizing agents while the ketones derived from secondary
alcohols are stable to further oxidation. (Lecture Notes, Mr. Asong 202)

In this experiment, we will show that a ketone can be prepared by the oxidation of a cyclohexanol,
using chromic acid as the oxidizing agent. Cyclohexanol has a significantly higher solubility in water
than cyclohexanone. The chromic acid is formed in one site by the reaction of sodium dichromate
and dilutes sulphuric acid which then reacts with the secondary alcohol. The reaction is more
commonly known as the Jones Reaction. The overall reaction is represented by the following
equation.

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Procedures

To start up the experiment, sodium dichromate dihydrate (12.5 g) was dissolved in water (60 mL) in
a 100 mL beaker and with continuous stirred with a glass rod; carefully and slowly concentrated
sulphuric acid (11 g, 6 mL) was added. Then the mixture was allowed for at least 7 minutes to cool.

Next, cyclohexanol (9.6 g) was placed in a 100 mL conical flask and the dichromate solution was
added to it one portion with swirling to ensure thorough mixing.
When the temperature rises to 55 °C, the flask was cooled in cold water; sufficient external cooling
have been applied to keep the temperature between 55 and 60 °C.
When the mixture no longer heats up, allowed to stand, with occasional swirling for an hour. The
mixtures were poured into a 250 mL round bottom flask, and there added 60 mL of water.
While waiting, a distillation apparatus were set up and a stopper was used instead of a thermometer
and a 100 mL graduated cylinder to collect the distillate.
Then the mixture was distilled using a Bunsen burner until about 30 mL of distillate has been
collected.

Next, the distilled mixture was transferred to an Erlenmeyer flask and saturated with salt (about 7.0
g NaCl). Then the layer of cyclohexanone was separated accurately in a separatory funnel. The
aqueous layer was extracted twice with 10mL ethyl acetate and the ethyl acetate extracts was
combined with the cyclohexanone layer.

Finally, combined solution was dried with anhydrous magnesium sulphate for at least 5 minutes and
filtered into a pre-weighed dry 50 mL round bottom flask.
The ethyl acetate was distilled off at boiling point 77 °C, using a distillation apparatus had been set
up by laboratory technicians on a steam bath. This leaves the cyclohexanone at boiling point 153-
156 °C in the flask. The weight of the product was successfully determined and hence the % yield
calculated as shown in the results. Before discarding the dark green chromium (III) sulphate solution
in the waste bottle provided, 2 mL ethanol was added and swirled wisely.

Results

Every experiment is carried out to come up with required results. Therefore, this experiment was
successfully completed and below shows is the results obtained at the end of this experiment. The
final product was cyclohexanone after the oxidation.

Mass of Glass = 48.89g

Mass of Glass + product = 52.5g
Mass of product = 52.5g – 48.89g = 3.61g

Boiling Point=153° - 156°

 Using these results, now calculate the theoretical yield and the percentage yield.

To find theoretical Yield, first we write the balanced chemical equations. Thus, below is the balanced
chemical equation for this reaction.

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Since 9.6g of cyclohexanol is used in this experiment, we convert this to mole by dividing by
molecular weight of cyclohexanol (100.0g/mol), 9.60g/100.0g = 0.096mol.

According to balanced chemical reaction, 3 moles of cyclohexanol should produce 3 moles of

cyclohexanone, therefore mole ratio should be 3:3 = 1:1 so 0.096mol of cyclohexanol should
produce 0.069mol of cyclohexanone.

Now we convert this mole into grams by multiplying by the molecular weight of cyclohexanone
(98.0g/mol).

0.096mol x 98.0g/mol = 9.408g 9.41g

Theoretical yield = 9.408g 9.41g
Now percentage yield = actual yield / theoretical yield x 100%
= 3.61g/9.41g x 100%
= 38.37%

Error = ± 61.63%

Interpretation of results/ Discussions

Oxidation of alcohols to form ketones or carboxylic acids is a fundamental and widely used reaction.
Primary alcohols can be oxidized to aldehydes or carboxylic acids while secondary alcoho ls oxidize to
ketones. Tertiary alcohols are resistant to oxidation. This experiment was successfully contacted
using Cr2O7 an oxidizing agent to oxidize cyclohexanol into cyclohexanone. This oxidation reaction is
exothermic, which means it releases heat to the environment as the reaction progresses. The
reaction can be considered complete when the reaction mixture cools back to room temperature.

The product (cyclohexanone) formed separate layer during the reaction. It was determined by the
density that the layer formed on the top (floats). Cyclohexanol has a significantly higher solubility in
water than cyclohexanone therefore ethanol was added because it is soluble with cyclohexanone
and lower boiling point makes evaporation easier.

The product, Cyclohexanone was a fine, clean colourless liquid. The percentage yield was calculated
as 38.37% which shows that the errors have encountered at any part of the experiment. Most
probably, the errors were encountered during the separation of the layers and also at distillation
part.

Summary Conclusion

This experiment was being allowed to carry out in a period of three hours in the laboratory. The
main aim of this experiment was to perform an oxidation reaction involving the inter-conversion of
cyclohexanol to form cyclohexanone using Cr2O7-2as reactant agent.
Thus, it would be able to obtain the results take place as the reactions proceeds in the respective
parts in the experiment. But here, cannot conclude by saying all results and calculations given are all
accurate, this is because some errors (estimated as 61.63%) have encountered at any part of this
experiment. For example, percentage yield should be exactly 100% but the yield of this experiment
was 38.37% due to some experimental errors. However, the experiment was contacted successfully
and the aim of this experiment was achieved as results are stated above. Probably the large
contributor to the error was from not accurately adding solutions in the respective reaction and can
be corrected easily.

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Note; Inspection of IR spectra of cyclohexanol and cyclohexanone was done on appendix pages.

QUESTIONS

Q1. Explain why ethanol is added to the residue in the distillation flask? Why is this important?
Chromium (III) sulphate is toxic can harm the environment. Thus, Ethanol is added because it is
soluble with cyclohexanone and lower boiling point makes evaporation easier. The ethanol vapour is
then cooled and condensed inside the condenser to form a pure liquid. When all the ethanol has
evaporated from the solution, the temperature rises and the water evaporates.

Q2. Research the reaction in textbooks and work out the reaction mechanism of this reaction.
Hint; the reaction that is happening here is the Jones (Oxidation) Reaction.

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Q3. Apart from the spectroscopic techniques, how would you test for the conversion of the
alcohol to the ketone? Research for the chemical tests that identify the presence or absence of a
carbonyl group;
There are a number of tests that can be used to identify the presence of a carbonyl group in a
compound. These rely on the oxidising nature of the various carbonyl groups.

a). Using Tollen’s reagent:

This reagent is prepared by warming a mixture of ammonia (aq) and silver nitrate (aq) to give
ammoniacal silver ion. These ions can be reduced by heating with aldehydes. This produces silver
metal which generally costs the inside of the test tube used to give a silver mirror. Ketone gives no
change to the reagent when mixed, because of their inability to be oxidised.

b).Using Fehling’s/ Benedict’s reagent

This is a two part reagent comprising of a solution of copper (ii) sulphate and an alkaline solution,
which when mixed with an aldehyde and warmed gently, give a red precipitate. The blue copper (ii)
ions are reduced to give a red precipitate of copper (i) oxide, again, this reagent has no effect on
ketones.

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Reference

 http://www.sciencemag.org/cyclohexanone

 .http://web.archive.org/web/20130409024601/http://cyclohexanol.com.au/

 Lecture Notes, Belly Asong 2020

 Organic Chemistry tenth edition, T.W. GRAHAM SOLOMONS & CRAIG B. FRYHLE (pp
752)

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