Experiment 6 Date: 1 March 2011

Title : Preparation of Cyclohexanone

Objective : Preparation of cyclohexanone via oxidation of cyclohexanol with chromic acid and
distillation, extraction and drying of the crude product.

Chemical Equation and Structural Formula of Organic Substances Involved :

Cyclohexanol Sodium dichromate Sulphuric acid Cyclohexanone

Molecular weight
100 262 98 98
(g/mol)
Moles of
Weight (g) 10.00 20.00 17.60 -

Moles (mol) 0.100 0.076 0.180 -

Limiting reagent Cyclohexanol - - -

9.8
Theoretical yield (g) - - -
cyclohexanol = 10 g / 100 g/mol
= 0.1 mol

Moles of sodium dichromate = 20 g / 262 g/mol

= 0.076 mol

Moles of sulphuric acid = 17.6 g / 98 g/mol

= 0.18 mol

Moles of cyclohexanone = 0.1 mol × 98 g/mol

= 9.8 g

3 mol cyclohexan one 98 g cyclohexan one

Theoretical yield = 0.1 mol cyclohexan ol × 3 mol cyclohexan ol × mol cyclohexan one
= 9.8 g cyclohexanone

Apparatus : Round-bottomed flask (50 mL, 250 mL), measuring cylinder (50 mL), beaker (100
mL, 250 mL), conical flask (50 mL, 250 mL), glass rod, dropper, spatula,
thermometer, thermometer adapter, Liebig condenser, rubber tubing, distillation
adapter, still distillation head, separatory funnel, funnel supporting ring, retort stand
with clamps, electrothermal heater, hot plate, fluted filter paper, oven, stemless glass
funnel, glass funnel, electronic balance, glass vial

Chemicals : Dehydrated sodium dichromate (20 g), concentrated sulphuric acid (9.6 mL),
distilled water (100 mL + 80 mL), cyclohexanol (10.6 mL), common salt, ether (25
mL), acetone, anhydrous magnesium sulphate, ice, boiling chips
Procedure :

Dehydrated sodium dichromate, Na2Cr2O7.2H2O (20 g) is weighed using an electronic balance in a

beaker. Distilled water (100 mL) is measured using a graduated measuring cylinder and poured into
the beaker containing the dichromate and stirred using a glass rod until it dissolve thoroughly.
Concentrated sulphuric acid (9.6 mL) is measured using measuring cylinder and mixed with the
dichromate solution in portions and stirred. The mixture is cooled in an ice bath. Cyclohexanol
(10.6 mL) is measured and placed in a 250 mL conical flask. The chromic acid mixture is poured
into the flask in portions and swirled. The temperature of the mixture in the flask is ensured to be
between 55°C and 60°C by either heating it using a hot plate or cooling it using the ice bath. The
mixture is left aside to cool on its own for 30 minutes. Meanwhile, a 250 mL round-bottomed flask
is clamped to a retort stand with an electrothermal heater beneath it. After the cooling time has
elapsed, the mixture is transferred into the round-bottomed flask using a glass funnel. Distilled
water (80 mL) is measured and added into the flask. Three pieces of boiling chips are also put into
the flask. The distillation apparatus is then assembled and set up. The still distillation head is
connected to a Liebig condenser and its exiting adapter, which are clamped to another retort stand
at a lower height. The thermometer together with its adapter is inserted into the still head, with the
top of the thermometer bulb aligned with the bottom of the side-arm of the still head. A 100 mL
beaker is placed under the exiting adapter to collect the distillate. Water is run through the
condenser from the pipe with the inlet near the exiting adapter and the outlet near the side-arm of
the still head. The mixture in flask is heated until 80 mL distillate is collected. The still head,
Liebig condenser and the exiting adapter are dismantled and their internal walls are washed with
acetone and put into an oven. Meanwhile, a piece of filter paper is folded into fluted form with
stemless funnel together put into the oven. Common salt (14 g) is added to the distillate to saturate
it. A separatory funnel is washed with distilled water before use and suspended using a supporting
ring clamped to a retort stand. The saturated distillate is poured into the separatory funnel with the
stopcock tap closed. The funnel is closed using stopper before being shaken gently. The funnel is
then inverted with finger over stopper and the stopcock tap is opened to release the pressure inside
the stopper, i.e. a hissing sound of gas released is heard. The shaking and venting of the funnel is
repeated a few times until the audible hiss is no longer heard. The funnel is put back into the ring to
allow the organic and aqueous layers to settle. The stopper is opened and the stopcock tap is turned
to a vertical position to drain the lower aqueous layer into a clean, empty 50 mL beaker. The upper
organic layer is drained into another empty 50 mL beaker. The aqueous layer is poured back into
the funnel and ether (25 mL) is added into the funnel to be is shaken and vented a few times. After
the organic and aqueous layers have formed, the aqueous layer is drained off into an empty beaker,
while the upper organic layer is drained into a conical flask and mixed with the organic layer from
the first extraction. A spatula of anhydrous magnesium sulphate is added into the flask and left for
about 5 minutes. The mixture is then filtered via gravity filtration using the fluted filter paper in a
stemless glass funnel into an empty, clean 50 mL round-bottomed flask. Three boiling chips are
added into the flask. The distillation components are taken out of the oven and assembled for a
second distillation. An empty glass vial is weighed and its mass is recorded. The mixture is heated
and the temperature is observed. Any distillate produced before 150°C is collected into an empty
beaker. Distillate produced in the range of 150°C – 156°C is collected into the vial. During the
process, the temperature that reaches to a point where it stops increasing within the 150°C – 156°C
range is taken as the boiling point temperature. The vial is weighed to obtain the net mass of the
product and labelled with details of the experimental results.
Observation :

Dehydrated sodium dichromate when dissolved in water and sulphuric acid produces an orange
solution (chromic acid).

Chromic acid mixed with cyclohexanol produces a blackish-green solution.

Mass of empty vial = 12.40 g

Mass of empty vial + cyclohexanone = 15.80 g

Net mass of cyclohexanone = (15.80 – 12.40) g

= 3.40 g

Characteristics of cyclohexanone : Colourless liquid

Experimental boiling point : 152°C

Distillation of crude cyclohexanone gave pure cyclohexanone (3.40 g, 34.69 %) as colourless liquid
with boiling point of 152.0°C (reference: 150.0 – 156.0°C).
Discussion :

In this experiment, oxidation of cyclohexanol, a secondary alcohol, will produce

cyclohexanone, a 6-membered cyclic ketone. The oxidizing agent used in this experiment is
chromic acid. In order to form chromic acid (H2CrO4), dehydrated sodium dichromate
(Na2Cr2O7.2H2O) (20 g) is dissolved in distilled water (100 mL) before adding concentrated
sulphuric acid (H2SO4) (9.6 mL). H2SO4 is not added straightaway but rather in portions as the
process is exothermic. The mixture is stirred to ensure that Na2Cr2O7.2H2O dissolves entirely in the
water and acid. The formation of H2CrO4 is as below:

Na2Cr2O7.2H2O + 4H2SO4 ↔ H2CrO4 + Na2SO4 + [Cr(SO4)3]3- + 5H2O

The H2CrO4 formed is orange which is then used to oxidize cyclohexanol to cyclohexanone.
Cyclohexanol is poured into the flask containing H2CrO4 which is then shaken to ensure that the
entire cyclohexanol has been reacted (Cyclohexanol is the limiting reagent in this case) and also to
distribute the heat of reaction uniformly throughout the mixture. The mechanism of the oxidation is
shown as below:

Step 1: Ionization of chromic acid to hydrogen and acid chromate ion

Step 2: Attack of electron-rich oxygen in cyclohexanol onto proton

Step 3: Attack by acid chromate ion

alkyl hydrogen chromate

(chromate ester intermediate)

As chromate ester is thermally unstable, it undergoes an elimination reaction where the Cr – O

bond cleaves and thus the formation of cyclohexanone via oxidation of carbinol carbon.

Step 4: Cleavage of Cr – O bond

Organic Chemistry (6th ed.) Wade, L.G., pg. 463

As chromous acid (H2CrO3) is unstable, it quickly disproportionates to the chromic ion, Cr3+. With
the presence of Cr3+, the mixture changes from orange to greenish-blue. Overall during the process,
the oxidation number of chromium (Cr) changes from +6 to +3, as shown in the equation below:

3C6H12O + 2H2CrO4 + 6H+  3C6H10O + 2Cr3+ + 8H2O

↑ ↑
Before reaction After reaction: +3
Negative charge on CrO4 = – 2
x + 4(– 2) = – 2, x = + 6

Depending on conditions, the mixture is either cooled using the ice-bath or heated using the hot
plate to maintain its temperature within the 55°C – 60°C range, as this is where the oxidation
process occurs at optimum conditions. The mixture is then left to cool by itself for 30 minutes,
whereby its temperature will decrease slowly after the entire cyclohexanol has reacted and that no
more heat is released. The mixture is added with a further 80 mL of water to dilute it and also to
form an azeotrope mixture with cyclohexanone and added with boiling chips before undergoing
distillation.

Distillation is use to separate the components of a liquid mixture. Components with lower
boiling points will evaporate which are later condensed back to liquid form after passing through
the cooled internal walls of the condenser. The exiting adapter connected to the Liebig condenser is
clamped at a lower height to ease the flow of liquid distillate into the beaker used to contain it.
Water is run throughout the condenser so that the gaseous distillate condenses into liquid form in
the condenser. The thermometer in the still distillation head is adjusted so that the top of the bulb is
aligned with the bottom of the side-arm, so that the entire bulb is moistened when the distillate
vapour is condensed on it and that the distillate is collected within the correct temperature range
(For the first distillation, the temperature is not observed). Addition of boiling chips into the round-
bottomed flask before the distillation process is to minimize the explosiveness of sudden boiling
should the compound in the flask is heated above its boiling point. The condenser and adapter are
washed with acetone instead of water. This is because any leftover organic compounds inside these
two components may be insoluble in water, while acetone is able to dissolve and remove most
organic compounds.

The distillate is mixed with a spatula of common salt (sodium chloride, NaCl) to saturate it.
NaCl dissolves easily in the solution to form hydrated sodium chloride which then absorbs water
from the azeotrope. At this juncture, the mixture forms two immiscible liquid layers. The upper thin
organic layer of pure cyclohexanone is pale yellow, while the lower pellucid (clear) aqueous layer
may contain a small quantity of cyclohexanone dissolved in water and acid. Therefore, during the
first extraction with the separatory funnel, both the organic and aqueous layers are retained in
separate containers. The aqueous layer undergoes a second extraction using ether as the extracting
agent. Ether is chosen since it is able to dissolve excessive sulphuric acid, water and possibly,
unreacted cyclohexanol. Furthermore, its boiling point of 34.5°C is far lower than that of
cyclohexanone (ref. 155.6°C) and will evaporate off first before cyclohexanone during the second
distillation. The elimination of cyclohexanol will avoid any possibilities of formation of hemiacetal
and hemiketal via reaction of unreacted cyclohexanol with acid, without affecting the yield. The
dissolving of sulphuric acid in ether is shown as below:

CH3CH2OCH2CH3 + H2SO4  CH3CH2O+H–CH2CH3 + HSO4-

During both extractions, the funnel is inverted and the stopcock is opened to release gases that
might have developed during the shaking of the funnel. This is done frequently until that no audible
hiss is heard due to releasing the pressure as the funnel is made of thin glass and might burst under
any slight pressure. Having dissolved the unwanted compounds, the ether extract of cyclohexanone
is combined with the organic layer from the first extraction, before added with a spatula of
anhydrous magnesium sulphate (MgSO4) as a drying agent to absorb water traces in the extracts.
MgSO4 has the capacity to absorb water at maximum 105%, thus an excellent drying agent.
Moreover, it absorbs water at a fast rate and is very suitable for nearly all organic liquids. Having
left it for 10 minutes to allow complete water absorption, the hydrated magnesium sulphate solid is
filtered off by gravity filtration as residue. The liquid should be poured onto the upper portion of
the filter paper as the larger surface area at this portion enables more rapid filtration, thus
increasing the efficiency of filtration. By folding the paper into fluted form, the rapidity of filtration
is increased as almost the entire surface area of the filter paper is being used. It also clogs up any
possible tiny pores in the filter paper so that the results of filtration are maximized.

A second distillation serves to maximize the yield of the pure product. Although the compound
was distilled, separated and dried, but it cannot be guaranteed that the compound obtained in the
experiment is completely pure. Thus, the last resort would be heating the compound until it reaches
its boiling point. Each compound species will only evaporate when it reaches its corresponding
boiling point temperature. Since the boiling point of cyclohexanone is somewhere between 150°C
and 156°C, therefore, any form of distillate that exits the adapter before and after this range is not
the pure wanted product. Only distillate collected within that temperature range is considered as
pure cyclohexanone in this experiment. In this case, ether and water which have boiling points of
34.5°C and 100°C respectively will exit the adapter first, followed by cyclohexanone within the
observed temperature range to be collected in a vial. The heating process continues until the
temperature reaches to a point where it does not increase for a certain period. That point is
considered to be the boiling point of the product as it is where the liquid phase is about to change
into vapour phase and where the temperature stops increasing momentarily.

Upon completion of the experiment, the percentage yield of the liquid product was found to be
34.69 %, as shown in the calculations below:

Experiment al yield
Percentage yield = ×100 %
Theoretica l yield

3.4 g
= ×100 %
9.8 g

= 34.69 %

The calculated value of the experimental yield was found to be less than the theoretical yield of
85%, as according to “Oxidation in Organic Chemistry” by Kenneth B. Wiberg (1965), meaning
that quite a low yield of the product is obtained. This is due to several possible factors as listed
below:

a. Cyclohexanone has a very high boiling point and that distillation cannot be conducted until
the round-bottomed flask dries up completely as it might crack. Because of this, what is left
inside the flask might contain a small quantity of pure cyclohexanone.
b. Oxidation of cyclohexanol is reversible, and therefore cyclohexanol might not have entirely
oxidized to cyclohexanone, thus decreasing the yield.
c. High temperatures and presence of excessive unreacted sulphuric acid during the distillation
prove to be suitable for formation of cyclohexene as a by-product. As cyclohexene has a
boiling point of 83°C and evaporates off before cyclohexanone, the yield is thereby
decreased.

In the process of determining the boiling point, it was found that the experimental boiling point,
i.e. 152.0°C, is located within the range of 150.0°C – 156.0°C. However, it cannot be deduced
straightaway that the product obtained is pure, owing to the factors listed previously.

Conclusion :

Oxidation of cyclohexanol by chromic acid produces cyclohexanone (3.40 g, 34.69 %) with a

boiling point of 152°C in the form of colourless liquid. The product is not exactly 100% pure, due
to the possibility of impurities in the product and also errors in techniques used during the
experiment.
References :

Hart, Harold; Schuetz, Robert D., (1972), “Organic Chemistry: A Short Course” 4th ed. United
States of America: Houghton Mifflin Company, 183 – 184.

Lehman, John W. (1981), “Operational Organic Chemistry: A Laboratory Course” 1st ed. Boston,
Massachusetts: Allyn and Bacon, Inc., 477, 507 – 509, 534 – 535.

Wade, L.G., Jr. (2005), “Organic Chemistry” 6th ed. United States of America, Pearson Education,
Inc., 462 – 463, 852.

CUBoulder Organic Chemistry Undergraduate Courses (no date found), “Physical Constants and
Hazards of Some Organic and Inorganic Compounds”. Retrieved February 18, 2006, from
http://orgchem.colorado.edu/pdffiles/physdata.pdf

Exercises:
1. How would you demonstrate by the following methods that your product is a ketone?
(a) Chemical tests
Ketones react positively with 2,4-dinitrophenylhydrazine, producing orange precipitate.
However, aldehydes also have the same chemical characteristics as shown below:

(Draw reaction with reagent)

Therefore, to differentiate between ketones and aldehydes, the Tollens test is conducted.
The Tollens reagent is a solution of silver – ammonia complex that oxidize aldehydes
easily to produce a silver mirror, while ketones do not react positively to Tollens
reagent.

Organic Chemistry (6th ed.) Wade, L.G., pg. 852

(b) Physical method

Infrared spectroscopy can be used to distinguish ketones. The C=O bond in ketone is
showed by a peak located between 1800 cm-1 and 1700 cm-1 or between 1725 cm-1 and
1705 cm-1 to be exact. However, peaks within the (1800 – 1700) cm-1 range might also
show that the product can be an aldehyde, a carboxylic acid or even an ester. To
confirm that the product is a ketone, the following observations can be made:
i. Absence of broad O-H peak between 3400 cm-1 – 2400 cm-1 rules out carboxylic
acid.
ii. Absence of two C-H peaks at 2850 cm-1 and 2750 cm-1 rules out aldehyde.
iii. Absence of strong C-O peak between 1300 cm-1 and 1000 cm-1 rules out ester.
Having made these observations, it can be confirmed that the product is a ketone.

2. Predict the product(s) formed when cyclohexanone reacts with excess methanol in the
presence of catalytic amount of acid.

Step 1: cyclohexanone + methanol  (HCl) methoxycyclohexanol + water

Step 2: methoxycyclohexanol + methanol  (HCl) dimethoxycyclohexane + water

Overall: cyclohexanone + 2 methanol (excess)  (HCl) dimethoxycyclohexane + 2 water