EXPERIMENT 1 RECRYSTALLIZATION OF VANILLIN

(4-hydroxy-3-methoxybenzaldehyde)

Purpose:

To purify the vanillin by recrystallization procedure and to determine the recovery percentage.
The purified vanillin samples will be evaluate through melting point on the next experiment.

Introduction:

Recrystallization is a technique utilizes the observation that the solubility of solids in liquids
usually increases dramatically as the solvent temperature is increased. A barely saturated
solution of the solid in the hot solvent is prepared and allowed to cool. The solubility
decreases as the temperature drops. Solid crystallizes back out upon cooling. These impurities
pass through the final cold filtration. Several steps are followed in a typical recrystallization.

A. Solvent selection ~ The solubility of the solid is tested in possible solvents until
desirable solvent properties are found (solid should have low solubility in the cold
solvent and high solubility in the hot solvent).
B. Dissolving of solid ~ The solid is dissolved in a minimum amount of hot (usually
boiling) solvent to prepare a saturated solution.
C. Hot filtration ~ If insoluble impurities are present (not in todays experiment) a hot
gravity filtration is preformed to collect the impurities.
D. Solution cooling ~ The solution is allowed to cool and solidification should occur.
Sometimes seeding, scratching or cooling in an ice bath is necessary to induce
crystallization.
E. Ice bath cooling ~ The solution is usually cooled with an ice bath to further decrease
the solubility of solid in the solvent.
F. Vacuum filtration ~ A Buchner funnel, a filter flask, and as aspirator are used to
collect the solid.
G. Washing the crystals ~ While the crystals are still in the Buchner funnel, they are
usually washed with ice-cold solvent.
H. Drying ~ The crystals are usually air dried to allow evaporation of solvent
I. Percent recovery ~ The mass of the recrystallized sample divided by the mass of the
starting solid times 100% is the % recovery.
J. Purity determination ~ The purity of the sample is usually determined by a simple
physical measurement such as melting point.

1
Procedure

1. Weigh into a 120 mL or 250 mL Erlenmeyer flask about 2 g of vanillin.

2. Add about 50 mL of water to the flask and stir vigorously.
3. Using a Bunsen burner, heat the solution just to the boiling point and stir until all the
vanillin dissolves.
4. Place the flask in an ice bath for 5 min and stir occasionally.
5. Place a properly fitted piece of filter paper in your Buchner funnel. Make certain that all
of the holes are covered. Wet the paper thoroughly with deionized water from your wash
bottle and vacuum filter your vanillin crystals. Rinse the Erlenmeyer flask once or twice
with 5 mL of ice-cooled water and use this water to wash the crystals in the funnel.
6. Empty the crystals onto a weighed piece of filter paper and place them in your desk for
drying, being sure they cannot spill.

Results and Discussions

1. Mass of crude vanillin + container = ___________

2. Mass of container = ___________

3. Mass of crude vanillin = ___________

4. Mass of paper = ___________

5. What is the percent recovery?

6. Why is the vanillin solution cooled in an ice bath before vacuum filtration?
7. How does the recrystallization procedure remove solvent soluble impurities?
8. What additional steps should be added to this procedure to remove impurities insoluble in
solvent?
9. Gravity and vacuum filtration separate insoluble solids from a liquid phase. The choice
depends on conditions. Suggest criteria you would apply to choose between them.
10. Suggest any ways you can think of improve any parts of this experiment

2
Vacuum filtration assembly. The filter flask is clamped and test tube is
inserted to collect the filtrate

3
EXPERIMENT 2 MELTING POINT DETERMINATION

Purpose

To take melting point using the capillary tube.

Introduction:

In previous experiment, the attempted were made to purify a sample of vanillin. Today you
will determine the melting point measurement, the success of the purification. Anytime a
compound is obtained from a natural or synthetic source, its identity must be determined and
or verified. Physical properties such as density and melting point are extremely useful for
verification purposes because they involve quick and accurate procedures. These properties
also provide a simple method of obtaining a rough indication of purity. At 5 C difference
between an experimental and an expected melting point for example, indicates that the sample
is approximately 95% pure. Each 1% (up to about 10%), very roughly, depresses the melting
point 1C. impurities not only depress melting point but broaden them. Thus, if compound A
is supposed to melt at 65 C but experimentally it is found that heating causes it to begin
softening at 57 C and total liquefy at 65 C, we report that sample has melting range of 57
62 C and is considerably impure. The fact that contaminants tend to depress melting points
enables one to distinguish between two compounds with the same melting point.

Procedure

Using the procedure described below, determine the melting point of samples A, B and C
below. For the mixed sample, add approximately equal amounts of each compound to mortar
and grind them together with the pestle before inserting them into capillary tube.

A. Crude vanillin from Experiment 1

B. Recrystallized vanillin from Experiment 1.

1. Fill the capillary tube by pressing the open end onto the powdered sample until there is
about a 0.5 1 cm length of sample in the tube.
2. Now drop the capillary tube, sealed end down, through a 1 m piece of 6 mm glass tubing
that is being held on a hard surface.
3. The impact of capillary with the hard seldom results on breaking and causes the sample to
drop to the bottom of the tube.
4. Repeat the dropping procedure until the sample is packed in the bottom of the tube.
5. Place the capillary tube in the sample holder of the melting point apparatus.
6. Press ON button and observed the plateau light. When the plateau light is on, press the set
button until the heat light turn ON.
7. Start to record the melting point sample when the heat light is ON.
8. Observe the sample through magnifying eyepiece part.

4
Results and Discussions

Melting Range C

1. Crude vanillin from Experiment 1 = ___________

2. Recrystallized vanillin from Experiment = ___________
3. 50% recrystallized + 50% phenyl carbonate = ___________

4. Compare your answer with literature melting point of 81 82 C of vanillin, comment on

the purity of the crude and recrystallized vanillin and also the success of your
recrystallization.

Melting point apparatus

5
EXPERIMENT 3 REACTIONS OF ALKANE, ALKENE AND
CYCLOALKENE

Purpose:

To identify an unknown hydrocarbon family through combustion, solubility, and reaction

analysis.

Introduction:

Hydrocarbons are compounds containing only the elements hydrogen and carbon. The vast
number of hydrocarbons is indicative of the number of different ways the carbon skeleton can
be arranged. The major uses of hydrocarbons are as fuels and solvents. The properties, which
make them ideal for such, will be investigated. The bonding patterns vary with each
hydrocarbon family (alkane, alkene, alkyne, aromatic). The difference in chemical reactivity
will be studied. Saturated hydrocarbons contain only single C-C bonds, so-called sigma
bonds. Unsaturated compounds contain at least between two carbon atoms is the so-called pi
() bond. In general, -bonds are more one C=C or CC (double or triple) bond. The second
and third bond reactive than -bonds. In many cases, the -bond will react and the -bond
will remain unaffected. Two useful tests for unsaturation in laboratory analysis are the
reaction with bromine and the reaction with potassium permanganate.
Test with Br2: The -bond of an alkene is extremely reactive toward addition of bromine. The
red color of Br2will disappear almost immediately in the presence of a C=C. In time many
alkanes and aromatic hydrocarbons will also decolorize bromine by a substitution reaction.
The time factor is important to distinguish the addition reaction of an alkene from a
substitution reaction.
Test with KMnO4(Baeyer Test): The -bond is also reactive toward the strong oxidizing
agent KMnO4. The purple color of KMnO4will disappear as it is reduced. Under neutral or
basic conditions a brown precipitate (MnO2) will be observed. Under acidic conditions the
colorless Mn+2is produced. In all cases, though, the purple color of the permanganate ion.

Procedure:

Each student will be assigned an unknown. As you are performing the classification tests on
known compounds, test the unknown also. At the end of the period you should be able to
identify the unknown.

Part A: Combustion of Hydrocarbons:

Caution: Be sure all loose hair is tied back and papers are safely away
from the reaction area.

Test the following for combustibility: Natural gas (predominantly methane), heptane, 2-
pentene, toluene, and cyclohexane. Toluene is the common name of methylbenzene which is
an aromatic compound. Because it is aromatic, you will observe properties unlike unsaturated
compounds.

6
1. Natural gas: Ignite your burner. Observe the flame.
2. Liquids: Place 1-2 drops (no more) on the end of the scapula. Carefully ignite it in the
Bunsen flame and immediately remove it from the burner. Observe the results. Note the
quickness of the reaction, the type of flame, and the residue (if any).

Part B: Solubility of Hydrocarbons

1. Place 10 drops of the hydrocarbon in the smallest test tube. Add 2 mL water, stopper and
shake. If there is only one layer, the hydrocarbon has dissolved in the water. If there are
two layers, the hydrocarbon has not dissolved. In some cases the hydrocarbon is lighter
than water, sometimes heavier. Note the relative densities.
2. Place 10 drops of the hydrocarbon in a small test tube. This time add 2 mL of
cyclohexane. Stopper, shake and observe.
3. Repeat Steps 1 and 2 for each hydrocarbon. Record results.
4. Dispose of waste in the proper containers. Organic solvents do NOT go down the sink.

Part C: Reactions of Alkenes:

I. Reaction with Bromine

Caution: Bromine gives severe burns on the skin. In case the bromine solution is spilled on
the skin, apply glycerol quickly to the affected area. Wash the glycerol off with soap and
water.

1. Place 5 drops of each compound to be tested in a clean test tube.

2. Add the bromine solution drop wise, shaking after each drop until 10 drops have been
added. The compound is saturated if the red color persists. If the red color disappears, the
compound is unsaturated. Most compounds will decolorize if allowed to stand 10-30
minutes by a substitution reaction. The disappearances of red color within 15 seconds
indicates unsaturation because bromine adds to the -bond. Discoloration of bromine is
a test for unsaturation.

II. Reaction with Potassium Permanganate:

1. Prepare a blank solution from 2 mL acetone in a test tube and adding two drops of purple
KMnO4solution. No reaction should occur. The color may be used for comparison with
the other hydrocarbons.

2. Prepare each sample test tubes as follows: 2 mL acetone (solvent), 4 drops of the liquid to
be tested, and 1-2 drops (not more) of KMnO4 solution. The result is evident after 5
minutes.

7
Results and Discussions

Part A Combustion of hydrocarbon

Compound Observation Balanced Equation

Methane (natural gas)
Heptane
2-Pentene
Toluene
Cyclohexane
Unknown

Part B Solubility of hydrocarbon.

Record miscible as +, immiscible as , note if density is> or less < than solvent (if less
dense the sample floats on the solvent)
Compound
Solubility in water Solubility in Cyclohexane
Miscible or Relative Miscible or Relative
immiscible density immiscible density
Heptane
2-Pentene
Toluene
Cyclohexane XXX XXX
Unknown

1. Write a generalized statement regarding the solubility of hydrocarbons in a polar solvent

(water) and a non-polar solvent (cyclohexane).
2. What conclusion can you make regarding the polarity of hydrocarbons?

Part C Reactions of Alkenes

Describe the color changes you observed and then conclude reactions or no
reaction.

8
 Compound Reaction with Br2 Reaction with KMnO4

Heptane
2-Pentene
Toluene
Cyclohexane
Cyclohexene
Unknown

1. Write a generalized statement regarding the solubility of hydrocarbons in a polar solvent

(water) and a non-polar solvent (cyclohexane).
2. What conclusion can you make regarding the polarity of hydrocarbons?

9
EXPERIMENT 4 COMPARING THE REACTION OF ALIPHATIC AND
AROMATIC HYDROCARBON

Purpose

To compare the reaction of aliphatic and aromatic hydrocarbon.

Introduction

Hydrocarbons, compounds that contain only carbon and hydrogen, can be classified into
several types, depending on their structure. Aliphatic hydrocarbons are divided into three
classes: alkanes have only single bonds, and are said to be saturated; alkenes and alkynes
have carbon-carbon double or triple bonds, and are said to be unsaturated. Aromatic
hydrocarbons are cyclic compounds whose structure is related to that of benzene, with six -
electrons in a six-member ring.
The following experiments illustrate some of the fundamental reactions of saturated,
unsaturated, and aromatic hydrocarbons. The three classes sometimes react differently toward
the same reagent, in which case it may be used to distinguish between them.

Procedure

Aliphatic Hydrocarbon
Bromine or 1. Put 1 mL portions of cyclohexane into two separate test
chlorine water tubes.
2. Add 10-15 drops of bromine or chlorine water.
3. After shaking the tubes, place one in the dark, (under the
counter) and expose the other to sunlight or a bright light for
a few minutes.
4. Then compare the colour of the two tubes. Test for the
presence of hydrogen bromide or hydrogen chloride by
holding a piece of moist blue litmus at the mouth of each
tube.
5. Add 1 mL of cyclohexene to a clean test tube.
6. Add 10-15 drops of bromine or chloride water, shake the tube
and observe the result.
7. Test for the presence of hydrogen bromide or hydrogen
chloride evolution.

Aqueous Potassium 1. Place 5mL of potassium permanganate solution in two

Permanganate separate test tubes.
(Baeyer's Test) 2. Add about five drops of alkane to one tube and the same of
alkene to the other test tube.

10
 3. Shake the tubes well for 1 -2 minutes, and note the results.

Sulphuric Acid 1. To each of two 2 mL portions of concentrated sulphuric acid

in separate test tubes add about 10 drops of alkane and
alkene, respectively.
2. Shake the tubes well and note the results.
3. Discard the contents by pouring them into a beaker
containing at least 50 mL of water.

Aromatic Hydrocarbon
Bromine 1. Add 1 mL of toluene to a small test tube.
2. To another, add a few iron filings, followed by 1 mL of
toluene, using the latter to rinse down any filings stuck on the
test tube walls.
3. To each test tube add three drops of bromine.
4. Place the tubes in a beaker of warm water for 15 minutes.
Observe the colour of each tube, and whether or not
hydrogen bromide was evolved and record the results.

Aqueous Potassium 1. To a test tube containing 1 mL of toluene add 2 mL of dilute

permanganate (2.0% w/w) potassium permanganate solution shake and
record the results.

Results and discussions

Describe the color changes you observed and then conclude reactions or no reaction.
Compound Reaction with Reaction with Reaction with Balanced
Br2 KMnO4 Sulphuric Acid Equation
Heptane

2-Pentene

Cyclohexane

Toluene

11
EXPERIMENT 5 SIMPLE DISTILATION

Purpose:

To determine the percent of ethanol content in commercial mouthwashes

Introduction

Distillation is an experimental laboratory technique that is used to separate and purify liquid
organic compounds. For most practical purposes, distillation is an effective technique to
purify a compound from contaminants, as long as that compound is the major component
(>95%)of the mixture.
The distillation process can be explained in simple terms. When a compound in the distilling
flask is heated to its boiling point temperature, a phase change from the liquid state to the gas
state is induced. The compound, in the gas phase, moves out of the distilling flask up into the
other parts of the distilling apparatus. When the gas vapors encounter the cold condenser tube
(below the boiling point temperature) of the distilling apparatus, the gaseous compound
reverts back to the liquid phase and drips into the collection flask.
One might assume that distillation of a 50:50 mixture of two components, say ethanol (bp 78
C) and water (bp 100 C), would follow a similar phenomenon, where the ethanol would
distill off first at 78 C, and the water would distill at100C. However, this is not what is
observed. The H-bonding interactions between the ethanol molecules and the water molecules
prevent a "clean" distillation from occurring. Instead, what occurs is the formation of an
azeotrope, a mixture of the compounds that co-distills in a specific molar ratio at a
temperature different from the boiling point of either of the individual components.
However, mixtures concentrated in one component can be achieved using this technique.
Consider commercial mouthwash, the ethanol-water mixture that will be used in this
experiment. Heating commercial mouthwash to ~78C will result in an azeotrope that has an
ethanol-water molar ratio of 95%:5%. A distillate collected at or around this temperature, will
contain mostly (95%) ethanol.

Procedure

1. Ethanol will be distilled from 20ml of a commercial mouthwash using a simple distillation
apparatus, depicted in Figure below.
2. There is also a simple distillation apparatus set-up in the laboratory for you to examine.

3. Set up a stirrer/hot plate and ring stand in the hood. Place a 50 mL heating mantle on the
stirrer.
4. Insert a 50mL round bottom flask (distilling flask) into the heating mantle and clamp the
neck of the flask to the ring stand.
5. Be sure to position the flask over the center of the stirrer plate.
6. Measure out exactly 20 ml of commercial mouthwash using an Eppendorf pipet and weigh
it. Record the weight.
7. Dispense the mouthwash into the distilling flask.

12
8. Add a magnetic stir bar to the flask and continue to set up the simple distillation apparatus
as shown in Figure below.
9. Attach a distilling head, thermometer adapter and thermometer.
10. Position the thermometer bulb just below the Y of the distilling head.
11. Place a second clamp on the apparatus at the joint between the distilling head and the
thermometer adapter.
12. (Never clamp anywhere except at the joints! It will crack the glassware.) Set up a second
ring stand.

Simple distillation apparatus

13. Attach a condenser and vacuum adapter using Keck clamps.

14. Attach a 25 ml round-bottomed collection flask and place a third clamp (clamped to a
second ring stand) at the joint between the vacuum adapter and the collection flask. Be
sure all the joints fit snuggly together, otherwise the apparatus will leak and reduce the
efficiency of the distillation.
15. Connect the water hoses to the condenser, with water in at the bottom, and draining
out to the sink at the top end of the condenser.
16. Connect the heating mantle to the Variac, and set the Variac at approximately 50V. Check
your apparatus against the diagram in Figure below, and the set-up in the lab before you
continue.
17. Carefully turn the water on, turn on the magnetic stirrer and the Variac (heat).
18. As the apparatus is heated, the mouthwash in the distillation flask will begin to bubble.
19. The temperature reading on the thermometer will not rise immediately.
20. The actual distillation will begin when the entire apparatus is saturated with the distillate
vapor.
21. As the vapor rises through the distilling head and encounters the condenser (which is cold
from the water running through it) the distillate will condense back to the liquid phase and
drip into the collection flask.

13
22. Monitor the thermometer temperature as the distillate drips into the collection flask.
Distillate should be collected when the thermometer reads 77-79C (calibrated and
corrected). (This is actually a ~95% ethanol-5% water azeotrope.).
23. When the temperature rises above 79C, turn the Variac off, remove the collection flask
and replace it with a second, clean flask.
24. Weigh a clean, dry 50 ml beaker and record the weight. Dispense the collected distillate
into the pre-weighed beaker and weigh it again to determine the weight of the distillate.

Results and Discussions

1. Calculate the percent recovery of ethanol from the total volume of mouthwash you
distilled. Show your calculations below.
2. What brand of mouthwash did your group distill? Using the table below, list your %
recovery of ethanol and the percent recoveries of ethanol others at your bench obtained
from the distillation of mouthwash. What is the average percent recovery?

14
EXPERIMENT 6 REACTION OF ALKYL HALIDES

Purpose

To observe qualitatively how factors such as electrophile structure, solvent and concentration
influence the rate of nucleophilic substitution.

Introduction
Nucleophilic substitution reactions constitute a very important class of organic process. In a
very general sense, these reaction involve:
A nucleophilic: an electron-rich species that forms a new bond to an electron-deficient
carbon atom in a molecule;
An electrophile: an electron-poor species that is attacked by the nucleophile and expels the
leaving group;
Leaving group: the ion or molecule that is displaced from the electron-deficient carbon of
electrophile by nucleophile.
There are two limiting mechanisms for nucleophilic substitution reaction; SN1 (first-order), in
which the leaving group departs prior to nucleophilic attack (often by the solvent; hence, this
process is sometimes called solvolysis), and SN2 (second order), where approach by the
nucleophile occurs at the same time as the leaving group is departing. These reactions are
highly dependent on the precise reaction conditions, as discussed in detail in your textbook.

Summary of information on SN1 and SN2 Reactions

UnimolecularNucleophilic
Substitution (SN1)
Kinetics First order
Mechanism Two-step (unimolecular in
rate-determining step)
Stereochemistry Racemization predominates
Reaction reactivity 3 o > 2 o > 1 o > CH3 >
vinyl
Rearrangements May occur
Effect of leaving group -I > -Br > -Cl>> -F
Effect of nucleophile Not important
Second-Order
Nucleophilic
Substitution (SN2)
Second order
One-step (bimolecular)
Inversion of configuration
3 o < 2 o < 1 o < CH3 <
vinyl
None
-I > -Br > -Cl>> -F
-I > -Br > -Cl> -F

Concentration of Favored by low conc. Favored by high conc.

nucleophile
Solvent polarity High favorable Low favorable

Procedure

General Procedure

15
1. Each test must be performed in a clean test-tube. If you rinsed out your test tube with
water, make sure that you rinse with ~0.25 mL of the solvent (ethanol or acetone) used in
the next test.
2. Do not contaminate reagents with samples or other reagents. Each reagent is provided
with a pipette, which should only be used with this specific reagent.
3. Perform tests on each of the alkyl halides provided;
1-chlorobutane,
1-bromobutane,
2-bromobutane,
t-butyl chloride,
crotyl chloride; (E)-1-chloro-2-butene
4. Examine the results to make sure that they make sense (for example, a 3 o alkyl halide
should not react via an SN2 mechanism faster than a 1 o alkyl halide).
5. Repeat tests if you are uncertain about the outcome.

Sodium iodide in Iodide ion is an excellent nucleophile and is soluble in acetone.

acetone These properties along with the non-polar nature of acetone favor
the SN2 reaction. The reaction can be followed since sodium
chloride and sodium bromide are not soluble in acetone and will
precipitate from solution.
1. Place 2-3 drops of each alkyl halide in individually labeled
reaction tubes, add 0.5 mL of an 18% solution of sodium
iodide in acetone, mix the contents thoroughly and note the
time.
2. Record the time of the first appearance of any precipitate. If no
reaction occurs within approximately 5 min, place the tube in a
~50 o C water bath.
3. Watch for any reaction over the next 20 min.
4. Record your observations. Rinse the reactions tubes with ~0.25
mL of ethanol before proceeding to the next test.

Ethanolic silver When an alkyl halide is treated with an ethanolic solution of

nitrate solution silver nitrate, the silver ion coordinates with an electron pair on
the halogen, weakening the carbon-halogen bond and resulting in
the formation of an insoluble silver halide. This reaction proceeds
via an SN1 mechanism. The nitrate ion is a very poor nucleophile
and ethanol favors ionization of the halide. As a result alkyl
nitrates do not form by an SN2 reaction.

1. Place 2-3 drops of each alkyl halide in individually labeled

reaction tubes as in part A of this experiment, add 0.5 mL of a
1% ethanolic silver nitrate solution, mix the contents well and
note the time of addition and the time of the appearance of the
first traces of any precipitate.
2. Again, if no reaction occurs with approximately 10 min, place
the tube in a ~50 o C water bath and watch for any reaction
over the next 10 min.

16
 3. Record your observations.

To test the effect of solvent on the rate of SN1 reactivity, compare

Solvent effects the time needed for a precipitate to appear when a 2-halobutane is
treated with 1% ethanolic silver nitrate solution (above) and when
treated with 0.5 mL of a 50:50 solution of water:1% ethanolic
silver nitrate solution.

Concentration To test the effect of concentration on the rate of SN2 reactivity,

effects compare the time needed for a precipitate to appear when a 2-
bromoalkane is treated with 18% sodium iodide in acetone at 50
C (above) and when treated with 0.5 mL of a 50:50 solution of
acetone: 18% sodium iodide in acetone and when 5-6 drops of 2-
bromoalkane is treated with 0.5 mL of 18% sodium iodide in
acetone and with 0.5 mL of the 50:50 solution, all at 50 o C.

Results and Discussions

Provide complete answers to the following questions in the spaces provided.

1. Arrange the following in order of increasing rate of substitution by the SN2

mechanism.
1-bromobutane, 2-bromobutane, 2-bromo-2-methylpropane
2. Arrange the compounds in question (i) in order of increasing rate of substitution by
the SN1 mechanism.
3. What would be the effect of carrying out the sodium iodide in acetone reaction with
the alkyl halides using an iodide solution half as concentrated?
4. Provide an equation, clearly showing the stereochemistry of the starting material and
the product, for the reaction of 2-bromobutane with sodium iodide in acetone.

17
EXPERIMENT 7 PREPARATION OF CYCLOHEXENE

Purpose

To prepare cyclohexene through dehydration of cyclohexanol using a strong acid via E1

mechanism.

Introduction

Dehydration of cyclohexanol to cyclohexene can be accomplished by pyrolysis of the cyclic

secondary alcohol with an acid catalyst at a moderate temperature or by distillation over
alumina or silica gel.
The procedure selected for this experiment involves catalysis by a strong acid (sulfuric acid,
phosphoric acid, and etc.). When a mixture of cyclohexanol and strong acid is heated in a
flask equipped with a fractionating column, the formation of water is soon evident. On further
heating, the water and the cyclohexene formed distill together by the principle of steam
distillation, and any high-boiling cyclohexanol that may volatilize is returned to the flask.
However, after dehydration is complete and the bulk of the product has distilled, the column
remains saturated with water-cyclohexene that merely refluxes and does not distill. Hence, for
recovery of otherwise lost reaction product, a chaser solvent is added, and distillation is
continued. A suitable chaser solvent is the water-immiscible, aromatic solvent toluene, boiling
point 110C; as it steam-distills, it carries over the more volatile cyclohexene. When the total
water-insoluble layer is separated, dried, and redistilled through the dried column, the chaser
again drives the cyclohexene from the column; the difference in boiling points is such that a
sharp separation is possible. The column holdup (retention of distillate) in the metal sponge-
packed column is so great that if a chaser solvent is not used in the procedure, the yield will
be much lower.
The mechanism of this reaction involves initial rapid protonation of the hydroxyl group by the
strong acid. This is followed by loss of water to give the unstable secondary carbocation,
which quickly loses a proton to water or the conjugate acid to give the alkene.

Procedure

1. Set up a fractional distillation apparatus (see Experiment 5), using 100 mL round-
bottomed flask as the distilling flask and a 25 mL round-bottomed flask as the receiving
flask. Do not pack the fractionating column. Keep the receiving flask in an ice-water bath
to reduce evaporation.

2. Place 10.4 mL ( = 0.96g/mL; 10.0 g) of cyclohexanol and 3.0 mL of concentrated

phosphoric acid in the distilling flask (via a funnel) and add a few boiling chips. Start
heating the reaction flask and collect approximately 6-8 mL of cyclohexene/water
distillate in around bottom flask that has been immersed in an ice-water bath.
3. Use a funnel to transfer the distillate to a separatory funnel and wash it with 10 mL of a
10% sodium hydroxide solution.
4. Transfer the (upper) organic layer to a 50 mL dry conical flask and add 0.5-1.0g of
anhydrous sodium or magnesium sulfate that has been weighed immediately after the
transfer of the organic layer. Cover with a watch glass and let stand for about 5 minutes.

18
5. Gravity filter the solution into a dry 50 mL round bottomed flask, and set up for a simple
distillation using dry glassware. Remember that the connecting adaptor, adaptor outlet and
condenser (used in sep 1) might contain droplets of water that have to be removed (by
washing with acetone) in order to obtain dry cyclohexene. The dark residue in the
distilling flask can be removed using milliliter of methylene chloride and a test tube brush.
6. Collect the fraction that boils in the range of 80-85 C in a pre weighed vial or test tube
that is immersed in an ice-water bath. Calculate the percent yield.
7. Perform the following test for unsaturation:
a. Add 5-10 drops of distilled cyclohexene to 0.5 mL of a 1% potassium permanganate
solution in a test tube.
b. Add 5-10 drops of distillate to 0.5 mL of 1% bromine water solution in a test tube.
8. Observe and record the results of these two tests, then compare them with the results
obtained when cyclohexane is used instead of cyclohexene.

Results and Discussions

1. Explain the purpose of the following in the above experiment

a. Phosphoric acid
b. Fractional distillation
c. Sodium hydroxide extraction
d. Anhydrous sodium or magnesium sulfate
e. Ice cooled receiving flask
f. Covering the flask with a watch glass in step 4.
2. Write balanced equations for the unsaturation tests of cyclohexene performed in step 7 of
this experiment. Use the half-reaction.
MnO4- MnO2 for (a).
3. Give all possible alkenes formed in the dehydration of the following alcohols:
1-methylcyclohexanol; 2-methlyclohexanol; 1-hydroxymethylcyclopentane;
3,3-dimethyl-1-butanol
4. What alcohol would be most appropriate for the synthesis of 1 methylcyclohexene? Write
an equation.

19