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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 when dissolved in water and sulphuric acid produces an orange
solution (chromic acid).
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 :
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:
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:
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:
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 :
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:
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.
2. Predict the product(s) formed when cyclohexanone reacts with excess methanol in the
presence of catalytic amount of acid.