The Organic Chemistry Laboratory

Selected Experiments for Organic Chemistry I

Department of Chemistry and Physics
Virginia State University
Petersburg, VA 23806
Fall, 2008

VIRGINIA STATE UNIVERSITY

DEPARTMENT OF CHEMISTRY AND PHYSICS
Tentative Syllabus for Organic Chemistry I Laboratory, Fall 2008
Chem 307-13 (Wednesday, 2:00 PM) and Chem 307-14 (Thursday, 2:0 PM)
Instructor: Dr. David Eggerding
Office: 243N Hunter McDaniel
Phone: (804) 524-5627
E-mail: deggerding@vsu.edu
Office hours posted on Blackboard and on the door to 243N Hunter McDaniel
Tentative Schedule of Laboratory Experiments and Examinations
Week of
8/18

Experiment Title
No Laboratory Meetings this Week Opening Week of Classes

8/25

Check-in, Syllabus, Course Requirements, Safety

9/1

Recrystallization of an Organic Compound and Melting Point

9/8

Separation of Acidic, Basic, and Neutral Compounds

9/15

Extraction of Caffeine from Tea

9/22

Simple and Fractional Distillation

9/29

Midterm Exam and First Notebook Grading

10/6

Steam Distillation: Extraction of Eugenol

10/13

No Laboratory this Week Fall Break

10/20

Thin Layer Chromatography

10/27

Column Chromatography Isolation of Chlorophyll Pigments

11/3

Phase Transfer Catalysis: Addition of Dichlorocarbene

11/10

Relative Reactivities of Aromatic Compounds

11/17

Final Examination and Notebooks are due.

11/24

No Laboratory Meetings - Thanksgiving Week

.

Course Description
Chemistry 307 (Organic Chemistry Laboratory) is the first of a two semester sequence which examines
the fundamentals of and practice of separation, purification, and the identification of organic compounds.
Textbook
All necessary material is contained in this Word Document.

GRADING POLICY
The course grades will be determined as follows:
Notebook, Prelabs, and Lab Technique
Midterm Examination
Final Examination
Total

56 points
20 points
24 points
100 points

Grades will be assigned according to the following scale:

90 -100
A
80 89
B
70 79
C
60 69
D
0 59
F
The Laboratory Notebook
A bound (marble) notebook is required for recording procedures, data, and observations made in the
organic laboratories. The notebook in a chemistry laboratory is regarded as a legal document and has
been used to settle patent and copyright disputes. I don't expect your notebook to be used to settle
patent disputes; however, whether or not you plan to pursue chemistry as an ultimate career objective, I
regard the development of the skills necessary for maintaining an accurate account of the progress of an
experiment in the laboratory as a major goal of this course. Therefore, the notebook will be collected
twice as indicated above for grading during the semester. The grading of the experiments in the
notebook will be based upon completeness and usefulness in reproducing any particular experiment
without referring to the text or other reference.
Your notebook MUST be set up as follows:
All entries in your notebook will be made in ink. Allow 3 pages at the front of the book for a table of
contents, which must be kept up-to-date. Number each page and do not leave any blank pages for
acquiring notes during the experiment.
Date the top of the page when you begin to make entries for each experiment. This date should be the
date you begin to set up the experiment prior to coming to the laboratory.
Give a short title to the experiment and enter it in the table of contents.
State the purpose (objective) of the experiment.
Write balanced equations for the reactions if any.
Reference the source of the experimental procedure: e.g. Gatrone, Title, Organic Chemistry Handout,
date
Enter each material used or produced in a table of quantities and physical properties. This table should
indicate the use of each material (reagent, catalyst, etc.), the molecular weight, the amount used (mass
and/or volume moles), the theoretical moles consumed or produced, and indicate the limiting reagent, the
concentration of each material in the solvent, and the physical properties (bp, mp, density, etc). No entry
should be made for moles used of a solvent.
Write the equations for the principal side reactions if applicable.
Summarize the procedure in sufficient detail that you can follow it without referring to the text or handout.
Do not copy the procedure verbatim from the text or handout or paste a photocopy into your notebook.
Note any hazards or precautions that should be observed. The use of a flow chart works well for this
summary.
Note waste disposal procedures that will be used for each material.

The entries to this point MUST be entered into your notebook prior to the start of
the experiment. After these entries are made you should date and sign the page.
Failure to have these entries made prior to the start of the laboratory is cause for
being asked to leave the laboratory. NO makeup labs are permitted.
You will be working in a group of two students. Each student is responsible for collecting their own data
and observations while the experiment is being conducted jointly. Record observations directly into the
notebook. Do not write on pieces of scrap paper or paper towels during the laboratory. If the use of
scrap paper or paper towels is observed your notebook grade will be reduced by 5% for each occurrence.
Record comments or suggestions made during the experiment in the notebook. If you make an error,
cross out the error with a single line and enter the corrected information. Do not use white-out or an ink
blot to make the error disappear. This section should not contain conclusions. Date and sign the page at
the end of the experiment. If a page is not completely filled draw a line diagonally through the empty
space and sign your name above the line to indicate the space was left intentionally blank.
If applicable calculate theoretical yield based on the actual amounts of materials used in the experiment.
If applicable calculate the percent yield or recovery.
If applicable write the mechanism of the reaction.
Analyze the data obtained and rationalize any discrepancies between the observed data and the
literature values.
Draw conclusions from the observed data. This section of the notebook should be written in a narrative
form using complete sentences and the active voice.
Notebook and Laboratory Technique Grading
Each of the nine experiments will count for a maximum of 7 points, and I will drop your lowest of your
nine scores. Thus, the maximum score will be 8 x 7 = 56 points. This allows you to miss one lab without
necessarily lowering your grade. The seven points will be apportioned as follows:
Prelab assignment
2 points
Lab technique
2 points
Notebook scoring
3 points
I will provide a brief discussion of the days experiment, emphasizing safety concerns, beginning at 2:05
PM. If you arrive later than 2:05, you will lose 1 point from your technique score. (If you arrive after 2:15
PM, you will not be allowed to enter and your score will be zero for this experiment.) Other technique
point deductions may be made for failing to follow instructions, unsafe practices, inadequate notebook
preparation, and having community equipment in your drawer. Occasional drawer inspections will be
done.
Prelab assignments will be distributed the week before you do the experiment. If you miss class, it is
your responsibility to see me to get a prelab assignment. I will not accept a photocopy of your partners
assignment.
Your notebooks will be graded twice, once following the midterm exam, and once following the final
exam. Notebook requirements are provided above.
Midterm Examination
A midterm examination will be given as indicated on the schedule. You will not be allowed to use your
notebook during the exam.
Final Examination
The final examination will be cumulative from the midterm exam to the end of the semester. You will not
be allowed to use your notebook during the exam.

Extra Credit
Extra credit will NOT be available at any time.
Attendance
Attendance in laboratory is required and attendance will be taken. The provision of dropping one lab
allows you one unexcused absence. Any additional absences will be recorded as zeroes for that lab
grade, and included in the calculation of your final lab score. If you miss a lab due to a documented
university-sponsored event, your final lab score will be prorated accordingly, and I will still drop your
lowest lab score.
If you miss more than three labs, regardless of your reasons, you will automatically fail the
course.
The laboratory begins promptly at 2:00. The door will be locked at 2:15 and entry will not be permitted.
Safety
You are expected to follow all departmental safety measures. A separate safety handout has been
provided to you. Please familiarize yourself with this handout as you can expect questions regarding this
material to appear on the Laboratory Quizzes and the Final Examination. A few very important points
will be addressed here:
Hair:

Long hair must be tied back at all times during the laboratory.

Eye Protection: Safety glasses or goggles must be worn at all times.

There are no exceptions to this rule.

Any student removing (includes lifting, wiping an eye, fogged glasses, etc.) their safety glasses or
goggles while in the laboratory for any reason or length of time will be summarily and immediately
dismissed from the laboratory. The student will receive a grade of zero (0) for that experiment. A second
violation will result in the student either withdrawing from the course or failing the course.

No warnings nor second chances will be given.

Clothing: Shorts, sandals, open-toe shoes, abbreviated shirts and tops and dangling jewelry are NOT to
be worn in the laboratory at any time. Any student inappropriately attired will not be allowed in the
laboratory. If the student is unable to get home or to their dorm, change, and return in time to finish the
laboratory the student will receive a 0 for that experiment.

There will be no warnings nor second chances given.

Additional Information
The Universitys policies on grading, academic honesty, and laboratory decorum will be enforced.
Students who are covered under the American Disabilities Act should privately inform me of this fact so
that appropriate instructional arrangements can be made.

Very Important Note

You must be enrolled in the lecture (CHEM305) or to have already taken CHEM305 successfully in
order to be enrolled in this laboratory. If during the semester you withdraw from the lecture, you
must also withdraw from the laboratory. No exceptions will be granted.

Acknowledgment of Receipt of Laboratory Safety and Procedures Manual and Syllabus

By my signature on this document I, ________________________________________________,
(Printed Name)
acknowledge receipt of copies of the following documents
Tentative Syllabus for Chemistry 307/308,
Laboratory Safety and Procedures Manual for Chemistry 307/308,
and
Laboratory Handout of Experiments for Chemistry 307/308
I also acknowledge that I have read these documents, that these documents were discussed in class,
and that I fully understand my responsibilities for my performance in this course. In addition, I
acknowledge the following safety rules:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.

The laboratory is to be used for serious work.

Do not perform unauthorized experiments.
Follow all instructions for use of safety goggles in the laboratory. Gloves will be provided if
needed. Read all laboratory instructions and procedures ahead of time to familiarize yourself
with the protective clothing requirements. Contact lenses should not be worn in the laboratory.
Long hair should be pulled back and secured with a band. Jewelry should be removed.
If you need to leave the room for any reason all experiments in progress must be supervised by
at your laboratory partner.
Books other than those required for the experiment and bookbags are not allowed in the
immediate laboratory area. The instructor will give directions for proper placement of these
items. Aisles must be kept clear for evacuation in case of fire or fire drill.
It is the responsibility of the student to read the laboratory directions before coming to class. If
you do not understand the directions, ask the instructor for assistance.
Know the location and use of available safety equipment in the laboratory, including fire
extinguisher, eyewash stations, fire blanket and first aid kit.
Report ANY accident, injury, or incorrect procedure to the instructor immediately.
If clothing should catch fire, smother it by rolling on the floor, use a fire blanket, and quench it with
water. NEVER RUN. Know the location of the fire exits. Know the location of the fire alarm.
Handle all materials under the direction of the instructor. If acid or other corrosive substance is
spilled, wash the area immediately with water. Keep combustible materials away from open
flames.
Never eat or drink anything in the laboratory. Never taste any chemical or draw materials into a
glass tube by mouth.
Place broken glass and solid substances into designated containers. Never wash any substance
down the sink unless it has been approved for such disposal by the instructor.
When the experiment is completed, turn off water and gas and disconnect electrical connections.
Clean all equipment and supplies and return to the proper area. Clean the work areas according
to the instructors directions. WASH HANDS at the conclusion of the laboratory experiment.
THE INSTRUCTOR WILL DETERMINE THE PENALTY FOR FAILING TO FOLLOW A
LABORATORY RULE. IF A STUDENT IS EXCUSED FROM THE LABORATORY FOR
VIOLATING ANY SAFETY RULES OR FOR BEHAVING IN AN UNSAFE MANNER THE
STUDENT MAY RECEIVE A ZERO (0) FOR THE ENTIRE COURSE.

I have read the material in this agreement and I understand my responsibilities as a student in the
laboratory. I agree to follow all safety rules and report any unsafe actions or procedures that I observe.
__________________________________
Student Signature

___________________
Date

Laboratory Safety and Procedures Manual

Department of Chemistry and Physics
Virginia State University
Organic Chemistry Laboratory
Laboratory safety is the collective responsibility of all persons working in a laboratory. The
laboratory is only as safe as the person practicing safety at the lowest level. For this reason it is the best
interests of everyone in the laboratory to keep alert regarding safety practices fro everyone in the room.
This is not a matter of informing on a friend or colleague, but of possibly saving a life. The first step
should be to mention the unsafe practice to the person doing it. If necessary, then report the practice to
the instructor in charge of the course.
General Safety Practices
The following general guidelines should be observed by anyone working in a scientific or
engineering laboratory:
1)
Understand and follow all safety instructions carefully.
2)
Be familiar with the location of all exits and available safety equipment, including fire
extinguishers, fire blankets, showers, eyewash stations, in your laboratory.
3)
Be familiar with the hazards associated with the chemicals and/or reaction you will be
using.
4)
Be familiar with the laboratory operations involved with the experiment(s) you are doing.
Frequently a laboratory operation may make a relatively harmless chemical dangerous.
5)
Never take, consume, or store food or drink in a laboratory. Never smoke, use, or open
tobacco products in a laboratory.
6)
Never apply cosmetics in a laboratory.
7)
Always wash you hands after using any chemical and before you leave the laboratory.
Frequent washing of hands is recommended during a laboratory exercise.
Personal Laboratory Safety
1)
Safety glasses or goggles must be worn at all times while you are in the
laboratory. Contact lenses are not acceptable for laboratory use and are forbidden.
2)
Clothing should be worn to protect as much of your body as possible without restricting
freedom of movement. Elegant and/or expensive clothes have no place in the laboratory.
High heeled shoes, open shoes, sandals, clogs, shorts, and abbreviated tops are not
allowed. You will not be allowed to participate in a laboratory experiment if your attire is
determined unsuitable by your instructor. You should wear shoes that protect the entire
foot, long pants, and shirts with long sleeves. A full length laboratory coat is a good
investment, although not required.
3)
Long hair must be tied back during the laboratory exercise. Hair is quite flammable.
4)
Do not wear jewelry.
5)
Never pipette any solution by mouth.
6)
Wear disposable gloves to handle chemicals, especially if you have allergies.
7)
Use the safety shower if a chemical spills on you or another person. Contaminated
clothing must be removed as quickly as possible. There is no room for embarrassment
in these situations as it could be a matter of life or death or serious disfigurement.
8)
If clothing catches on fire, drop to the floor and roll to extinguish the flames. Do NOT run
to the fire blanket or shower.
9)
The instructor must be notified immediately in case of any injury regardless of perceived
importance or size.
10)
If a burning sensation occurs in the eyes or skin, even after the laboratory is completed,
wash the eyes with copious amounts of water and the skin with soap and water. Contact
the University medical personnel immediately.
11)
In the event of any accident in the laboratory, leave the room as quickly as possible.
Inform your instructor and let more experienced personnel correct the situation.

General Laboratory Practices

The best safety rule in the laboratory is to be prepared for the laboratory. Prior preparation will
allow you to work at the optimum pace to complete the laboratory assignment in a timely and careful
manner. Working too slowly or rushing to finish are equally dangerous acts. Accidents are avoided by
careful planning and preparation. The unannounced laboratory quizzes in the course are designed to
test your preparation for the days experiment.
Upon reading this manual you should realize that the laboratory rules are based upon common
sense and are simply statements of this principle. When common sense is combined with sound
scientific information, Good Laboratory Practices (GLP) result.
1)
2)
3)
4)
5)
6)
7)
8)
9)
10)
11)
12)
13)
14)
15)

The laboratory is no place for horse play or rowdy behavior.

Never work in a laboratory alone.
All chemical should be treated as potentially dangerous.
Always add acid to water.
Only properly labeled materials should be used. Unlabeled or improperly labeled
materials are especially dangerous.
Never leave a laboratory experiment unattended. If you need to leave the room,
someone should be told and must watch your experiment.
Never heat a closed system.
Dispose of waste material promptly and in an approved manner. Knowledge of the
correct disposal procedures is part of the laboratory preparation.
Never taste or smell any chemical.
Always clean your work area during and especially when you are finished with the
experiment.
Keep drawers and cabinet doors closed. Open drawers and doors are a hazard to those
passing through and are an obstacle if the laboratory needs to be evacuated.
Never heat a flammable liquid in an open container nor with an open flame.
Visitors are NOT allowed in the laboratory.
Broken thermometers are especially hazardous as they contain mercury. You must
inform your instructor immediately so that cleanup can be done by someone with more
experience.
Broken glass should be placed in the proper receptacle.

General Safety Information

1)
The Environmental Protection Agency classifies waste material based upon their reaction
properties. There are currently four reaction classes: Ignitable materials (flammable liquids or
solids); Corrosive materials (acids, bases); Reactive materials (includes metals that react with
water, materials that form HCN, hydrogen gas, or other explosive materials); Toxic materials (it
should be noted that all materials are assumed to be toxic). Disposal should not be attempted
until the properties of the material is determined.
2)

Laboratory fume hoods are primary resources for safety as they remove noxious and/or toxic
materials from the room. The hoods should be turned on with the door half open.

3)

Insertion of a glass tube or rod into a stopper or flexible tubing is a common laboratory practice,
which can lead to serious cuts and injuries. To avoid these accidents, be certain that the
diameter of the tube and hose or stopper are compatible; lubricate the glass with water or
glycerol; hold the rod or tube no more than 3 cm from the end; slowly insert the tube with
minimum forcing; use a twisting motion to move the tube into the hose or stopper.

4)

Glassware must be assembled and care must be exercised in order to minimize breakage and to
reduce injury. Accidents are avoided by keeping your work area uncluttered; the use of clean,
dry glassware, choosing the correct glassware size for the assignment; not using broken,
cracked, or chipped glassware; properly lubricate glassware joints, and never heat a closed
system.

5)

Check electrical cords for frayed or loose parts before using.

Experiment 1
Recrystallization of an Organic Compound and Determining Its Melting Point
Recrystallization is a common technique used by organic chemists to purify
organic solids. The technique is dependent upon a particular compound having greater
solubility in a hot solvent than a cold or room temperature solvent. Cooling a saturated
solution causes the solid to precipitate from the solvent. Recrystallization is the process
whereby a solid compound is dissolved in a suitable hot solvent, from which impurities
can be removed by filtration and/or using decolorizing charcoal with filtration, followed
by allowing the solution to cool forming a saturated solution from which the purified
compound forms crystals.
Obviously the most critical aspect of the recrystallization process is the choice of
a suitable solvent. The solute should have high solubility in the hot solvent and low
solubility in the cooled solvent. Frequently the choice of solvent is made empirically
through trial and error although the principle of like dissolves like relates the molecular
structure of the solvent and the solute.
Experimental Procedure
You are going to recrystallize phthalic acid, an organic acid commonly used in
the preparation of polymeric materials, such as Dacron. Its structure is:
CO2H

CO2H
Phthalic acid is very soluble in hot water (18g/100mL) and is considerably less soluble
in cold water (0.54g/100mL at 14oC) making water an excellent solvent choice for the
recrystallization of phthalic acid. Prior to coming to lab you should calculate the amount
of boiling water necessary to dissolve 1 gram of phthalic acid.
Place 1.0 g of phthalic acid in a 50 mL Erlenmeyer flask. Add 4 5 mL of water
to this flask, a wooden boiling stick, and heat the mixture on a hot plate. After the water
begins to boil, slowly add additional water dropwise to the flask until the solid has
dissolved. Remove the flask from the hotplate and remove the boiling stick. Allow the
solution to slowly cool, undisturbed, to room temperature. You should observe crystal
growth. When the flask has reached room temperature, cool it further by placing it in an
ice bath for 10 15 minutes.
Set up a vacuum filtration apparatus using the filter flask and a Hirsch funnel and
collect the crystals by vacuum filtration. Wash the crystallized phthalic acid using cold
water. The crystals should be allowed to dry on a watch glass in your laboratory drawer
until the next laboratory period. You will determine the mass of the crystals you
recovered, the percent recovery, and the melting point of the phthalic acid.

Experiment 2
Separation of Organic Compounds by Extraction
Separation of acidic, basic and neutral products from each other takes advantage
of the different chemical and physical properties of the salts of the acidic and basic
functional groups. Organic acids are insoluble in water but soluble in a less-polar
organic solvent like diethyl ether (ether). Therefore, in a separatory funnel the
carboxylic acid would reside primarily in the ether layer. When a basic solution is added
to this separatory funnel the acidic proton would be removed forming a carboxylate salt
which is now water soluble and insoluble in ether.
A similar solubility trick can be used to extract basic compounds like amines. A
water soluble salt can be prepared by protonating an amine with an aqueous solution of
hydrochloric acid. The amine would than no longer be soluble in an ether solution. The
salts solubility can be reversed by contacting the ammonium salt with an aqueous
solution of base, such as sodium bicarbonate.
Sodium bicarbonate is a sufficiently strong base to deprotonate most carboxylic
acids. The slightly less basic phenols require aqueous solutions of sodium hydroxide to
remove the acidic proton.
Neutral organic molecules would not react with either the basic nor acidic
solutions and would remain in the organic solution. It is conceivable that a mixture of
materials could be removed and recovered by contacting with either acidic or basic
solutions. The following is a generalized flowchart for separating acidic, basic, and
neutral compounds.

Dissolve mixture in ether

RCO2H + ArOH + RNH2 + RH
acidic
phenol basic neutral

extract with HCl

aqueous layer

organic layer
RCO2H + ArOH + RH
acidic
phenol neutral

Ammonium salt

add NaOH

NaHCO3
organic layer

RNH2
carboxylate salt

ArOH + RH
phenol neutral

add HCl
add NaOH
organic layer
RH

RCO2H
aqueous layer
phenoxide salt
add HCl
ArOH

Experimental Procedure
You will separate a mixture that contains benzoic acid, naphthalene, and 4chloroaniline using the techniques discussed above. 4-chloroaniline is a basic material
that can be extracted into water using hydrochloric acid. Benzoic acid is an acidic
material that can be extracted into water using an aqueous solution of sodium
bicarbonate. Naphthalene is a neutral organic material that will remain in an organic
solution. You should write a flow-chart that demonstrates the proposed separation of
these three compounds prior to lab. When doing extractions in the laboratory it is
generally a very good idea not to discard any layers until the experiment is complete.
Be sure to label all flasks.
Place 3 g of the mixture in a 50mL Erlenmeyer flask and add 30 mL of diethyl
ether and gently swirl until the mixture is dissolved. Transfer the solution to a 125 mL
separatory funnel using a small amount of ether to assist with the complete transferal of
the mixture. Pour 10 mL of water into the separatory funnel and determine which layer

is the organic layer. Remove and discard the aqueous layer. Add 10 mL of 3M HCl.
Note which layer is the organic. Stopper and gently shake the separatory funnel. Be
sure to vent the vapors through the stopcock. Allow the layers to disengage and
remove the aqueous layer into a 50mL Erlenmeyer flask. Add 5mL of water to the
separatory funnel and shake. Combine this layer with the acidic layer from the previous
extraction and label the flask A.
Add 10mL of 5% aqueous sodium bicarbonate to the separatory funnel, shake
the mixture, making sure you vent as above, and allow the layers to disengage. Drain
the aqueous layer into a 50 mL Erlenmeyer flask and label this flask B.
The ether layer should contain any neutral organic materials. However, it also
contains an appreciable quantity of water. The water can be removed by extracting with
a saturated sodium chloride solution. Add 15 mL of saturated sodium chloride, gently
shake, and vent the separatory funnel. After the phases have disengaged, drain the
aqueous layer from the separatory funnel. The ether layer is poured through the top of
the separatory funnel into a 50 mL Erlenmeyer flask, labeled C and dried by adding
anhydrous magnesium sulfate to the ether solution.
Slowly add 8M sodium hydroxide to flask A. Test the pH of the solution using
indicator paper until it has a pH greater than 12. Cool the flask in an ice bath. Isolate
the acidic organic compound by vacuum filtration using a Hirsch funnel. After drying on
a watch glass for one week, record the mass isolated and the observed melting point.
Slowly add concentrated hydrochloric acid (CAUTION Corrosive) to flask B until
you have a pH approximately equal to 2. Test the pH of the solution using indicator
paper. Cool the flask in an ice bath and collect the basic organic material using vacuum
filtration and a Hirsch funnel. After drying on a watch glass for one week, record the
mass isolated and the observed melting point.
Evaporate the ether in flask C using a steam bath to obtain naphthalene.
Recrystallize the crude naphthalene from a hot solution of 3:1 methanol:water that you
need to prepare. Allow the solution to cool slowly to room temperature and then in an
ice bath. Collect the solid naphthalene using vacuum filtration on a Hirsch funnel.
Record the mass of naphthalene and its melting point

Experiment 3
The Isolation of Caffeine from Tea
Caffeine will be extracted from tea leaves in this experiment. Caffeine which
makes up about 5% by mass of tea leaves is relatively soluble in water. Therefore, it is
readily extracted from the complex structure of the tea leaves using hot water. Caffeine
is readily separated from the other water soluble compounds present in tea leaves using
methylene chloride (CH2Cl2) leaving the additional more water soluble materials in the
tea leaves behind. Evaporation of the methylene chloride (bp = 40 oC) using a steam
bath provides nearly pure caffeine.
O
H3C
O

N
N

CH3
caffeine

CH3
Experimental Procedure
A strong tea solution is prepared by placing 5 g of loose tea leaves, 2 g of
calcium carbonate powder, and 50 mL of water in a 100 mL round bottom flask
equipped with a condenser for reflux. The mixture is gently refluxed for about 20
minutes using a heating mantle. The hot mixture is vacuum filtered using a Buchner
funnel using a 125 mL filter flask.
After cooling the tea solution to room temperature, the tea solution is extracted
with 10 mL of methylene chloride using a 125 mL separatory funnel. The mixture is
gently shaken while venting the stopcock. After the phases disengage the methylene
chloride layer is removed. This extraction procedure is repeated 4 times and the
combined methylene chloride layers are placed in a 100 mL Erlenmeyer flask and dried
over anhydrous magnesium sulfate. The magnesium sulfate is removed by gravity
filtration using fluted filter paper into a 100 mL Erlenmeyer flask.
The methylene chloride is evaporated using a steam bath under the hood. The
resultant residue after the methylene chloride is evaporated is crystallized. The residue
is dissolved in a very small amount of hot acetone. After all of the residue is dissolved
petroleum ether is added dropwise until the solution becomes cloudy. The solution is
cooled to room temperature, then in an ice bath, and the caffeine crystals are collected
using vacuum filtration on a Hirsch funnel. The collected crystals may be washed using
a small amount of cold petroleum ether. Determine the mass of caffeine collected, its
percent recovery based upon the starting amount of tea, and melting point.

Experiment 4
Simple and Fractional Distillation
You will separate a two component mixture using two types of distillation simple
and fractional. The setup of the equipment used for this experiment is:

simple distillation

fractional distillation

Experimental Procedure Simple Distillation

Obtain a 50 mL sample of an unknown two-compound mixture from your
instructor. Be sure to record the letter of your unknown mixture. Place 10 mL of your
unknown in a 25 mL round bottom flask and set up the glassware as shown in the
above figure for a simple distillation but use a 10mL graduated cylinder for your
collection flask.
Start recording the temperature when the first drop of liquid drops into the
collection flask and every 0.4 mL thereafter. Stop heating when you have collected 8
mL of the distilled liquid. Plot the temperature (vertical axis) versus the volume of
distillate (horizontal axis). Extrapolate the plot to 10 mL. Indicate the identity of your
unknown mixture based upon the boiling points of each component and the percent
composition. Repeat the simple distillation.
Repeat the above distillation using a fresh 10 mL of your unknown and the
fractional distillation setup. Record the temperature after each 0.4mL of liquid collected
as long as the temperature remains constant. When the temperature begins to rise
record the temperature every 0.2mL. Stop distilling after you collect 4 constant
temperature readings at the higher temperature recording or after you have collected 8
mL of liquid. Repeat this process.
Plot T vs V as previously and identify the two components and the percent
composition in your unknown. The percent composition is determined by drawing a
vertical line through the midpoint of the increase in the temperature of each plot. The
volume at that point is that of the lower boiling component. The volume after that point
extrapolated to 10mL is the volume of the higher boiling component, unless an
azeotrope formed.
Azeotropes are systems of two or more organic liquids that boil at a constant
temperature different from the boiling point of either component. If an azeotrope forms
you must correct the volume of each component present in the azeotrope in order to
determine the percent composition.
Your report should contain the data obtained for each distillation, the plots you
made, your calculations of the percent composition of the unknown mixture, the identify
of the unknown components, and a comparison of the effectiveness of the two
distillation procedures.

Possible Components and Boiling Points (oC)

Acetone
56.5
Methanol
64.7
Isopropanol
82.5
Water
100.0
Toluene
110.8
n-Butanol
117.8

Possible Azeotropes
Acetone/Methanol
Acetone/Water
Methanol/Toluene
Isopropanol/Water
Isopropanol/Toluene
Water/Toluene
Water/n-Butanol
Toluene/n-Butanol

Boiling Point (oC) and Percent Composition

55.7
88.0/12.0
56.1
88.5/11.5
63.7
72.4/27.6
84.0
87.8/12.2
80.6
58.0/42.0
85.0
20.2/79.8
93.0
45.5/54.5
105.6
73.0/27.0

Experiment 5
The Isolation of Eugenol Steam Distillation
The total vapor pressure contributing to the boiling point of a mixture of
compounds is a combination of the two vapor pressures of those liquids. Therefore, the
total vapor pressure of two immiscible liquids would make the boiling point less than the
lowest boiling solution. If one of the two liquids were water, the boiling point would be
lower than water. This technique, referred to as steam distillation, allows chemists to
remove higher boiling materials at boiling points at 100 oC or less. This technique is
commonly used in the isolation of essential oils for the food and perfume industries.
Eugenol is a major component of clove oil and is readily isolated from clove oil.
Clove oil is effectively extracted from ground cloves by steam distillation. In this
experiment we will steam distill ground cloves to provide clove oil. We will remove
eugenol from the clove oil by taking advantage of the weakly acidic phenolic proton
according to the following reaction:
O- Na+
OH
OMe
OMe
NaOH
HCl

The water soluble eugenol anion is separated from the other constituents in clove oil
and the reaction is reversed by neutralizing the salt with hydrochloric acid to provide
pure eugenol.
Experimental Procedure
A simple distillation apparatus is assembled using a 50 mL round bottom flask
and a 25 mL Erlenmeyer flask as the receiver. The flask is charged with 0.5 g of ground
cloves and 25 mL of water and is heated to provide a steady distillation of water with a
constant temperature between 90 100 oC. Water may be added to the distilling flask
if necessary. You should collect between 20 25 mL of distillate.
The distillate is placed into a 125 mL separatory funnel and 5 mL of methylene
chloride is added. After shaking and allowing the phases to disengage, the organic
phase is transferred to an Erlenmeyer flask. The aqueous phase is re-extracted with 2

X 5 mL of methylene chloride in the same manner. The combined methylene chloride

solutions are returned to the separatory funnel and extracted with 2 X 4 mL of 5%
NaOH. A 20% aqueous HCl solution is added to the combined basic layers until the
solution is acidic to pH paper.
The acidic solution is extracted with 2 X 4 mL of methylene chloride. The
combined methylene chloride solutions are dried over anhydrous magnesium sulfate for
5 minutes. The dried organic solution is filtered (gravity) through fluted filter paper into a
pre-weighed 25 mL Erlenmeyer flask. The methylene chloride is evaporated on a
steam bath to provide Eugenol. Calculate and report your percent recovery based upon
the mass of gloves you used.

Experiment 6
Thin Layer Chromatography
The most modern method available for the separation of a multicomponent
mixture involves chromatography. Chromatography involves the distribution of two or
more components (ions, compounds) between two phases, one of which is stationary
the other moving. A variety of chromatographic methods have been developed and
include: solid-liquid (column, thin layer, and paper); liquid-liquid (high performance
liquid chromatography); and gas-liquid (vapor phase).
The chromatographic experiment works on the same principle as solvent
extraction where the efficiency of the separation is dependent upon the different
solubilities or adsorptivities of the substrate relative to the two phases. In this
experiment we will examine the use of solid-liquid chromatography for separating and
identifying the components in a mixture.
Thin layer chromatography (and column) is based upon both the adsorbitivity and
solubility of a compound as it partitions itself between a liquid (mobile) phase and a solid
phase. The solid phase may be any material that does not dissolve in the liquid phase.
The most common materials in use are hydrated silica gel (SiO2), hydrated alumina
(Al2O3), fluorisil (MgSiO4), and cellulose. The major difference between column and thin
layer chromatography is the amount of material used in the experiment. Frequently
both techniques are used simultaneously to accomplish a separation. TLC uses very
small scale (microgram to milligram amounts) while column chromatography uses
milligram to multi gram quantities.
Certain solid surfaces absorb thin layers of organic compounds as a result of
electrostatic forces. Because the strength of this absorption differs with the properties
of the solid support and the functional groups present in the organic compound, a given
solid may absorb each component of a mixture of organic compounds with varying
strengths. The features of a given component of a mixture determines the strength of
the absorption on the solid surface are very similar to those that determine the solubility
of the component in a given solvent. Molecules with strong dipoles absorb strongly on
polar surfaces and weakly on non-polar surfaces. They are also more soluble in polar
solvents than non-polar solvents. The converse is also quite true. The coupling of
these phenomena have been utilized to effect separations of components on a solid

support using thin layer chromatography.

In principle this may be accomplished by absorbing a mixture onto a solid
support and washing fresh solvent over the solid support permitting the molecules in the
mixture to be continually dissolved in the solvent and reabsorbed onto the solid. The
component less strongly absorbed will move with the solvent more quickly thereby
effecting a separation. The chromatography experiment is in effect a competition
between the compounds being analyzed and a developing solvent for both adsorption
on the solid support surface and the formation of a solution. As the solvent and the
solute compete for the active sites on the surface, a separation is observed.
Polar molecules determine the energy of adsorption primarily through the relative
polarities of the solute and the solvent for the polar surface. Since high polarity
molecules are preferentially adsorbed on a polar surface, a solvent of low polarity will
not re-dissolve them very effectively. In this case the solute will move very slowly as it
interacts with the solid support. However, in very polar solvents the solvent will also
absorb very strongly on the surface, displacing the solute and effecting very rapid
movement through the solid support. The following table indicate the relative polarities
of various solvents and commonly encountered compounds:

Solvents
(polarity increases down table)
Petroleum ether
Cyclohexane
Carbon tetrachloride
Toluene
Chloroform
Methylene chloride
Diethyl ether
Acetone
Ethanol
Methanol
Water
Acetic acid

Elution Sequence for Compounds

hydrocarbons (fastest)
olefins
ethers
halocarbons
aromatics
ketones
aldehydes
esters
alcohols
amines
acids
strong bases (slowest)

As the solvent flows up the plate the solutes are redissolved and readsorbed in amounts
proportional to the adsorptivities and solubilities of the components. As the solvent
passes through the plate, the cycle of adsorption dissolution is continued and the
various components of the mixture move in concentrated bands or spots. The least
tightly bound material moves ahead while more tightly held components trail behind and
a separation is effected.
Experimental Procedure
You will receive an unknown mixture from your instructor. Record the number on
the test tube you receive. The mixture you receive will contain 2 3 of the following
compounds:

benzanilide

benzil

benzoin

salicylamide

acetanilide

caffeine

acetophenetide

9-fluoreneone

4-chlorobenzophenone

You need to prepare 15 20 spotters. These are prepared from disposable

Pasteur pipettes by heating the pipette in a Bunsen burner flame and pulling the
softened glass to approximately arms length. The spotters are broken into
micropipettes approximately 5 cm in length.
It is recommended that you determine an effective solvent system for the
unknown compounds provided to you before you attempt to identify your unknown. This
is accomplished by dissolving approximately 5 mg (spatula tip) of the unknown in
methylene chloride and spotting a tlc plate with the solution about 1 cm from the end of
a plate.
The tlc plate is placed in a developing chamber containing the solvent chosen
(about 0.5cm of solvent) and a filter paper wetted against the side of the chamber. A
250 mL beaker is a perfect developing chamber. The chamber is covered with a watch
glass. The solvent level must be below the spots on the plate. The solvent is allowed
to travel up the plate (capillary action). The plate is removed from the chamber to dry.
Be sure to mark the topmost level of the solvent with a pencil mark.
After air drying the plate the eluted compounds are visualized using a uv lamp
followed by placing the plate in an iodine chamber. The compounds will show as
discrete spots that have moved away from the original spot. An Rf value is calculated
for each spot. This is done by dividing the distance the spot moved (in cm) by the
distance the solvent moved. See plate:
solvent front

final spot location

spot origin
solvent start

You must determine the optimum solvent polarity to effect a separation of your
unknown. This is done by examining various solvents of varying polarities according to
the earlier table. To minimize waste it is recommended that you try the following
solvents in increasing polar order: hexane, methylene chloride, acetone, and ethyl
acetate. You may wish to modify the polarity of the solvent by trying varying amounts of
a mixed solvent system, e.g. 90:10 hexane:ethyl acetate or 50:50 methylene
chloride:acetone.
After you have determined the optimum solvent and the number of components
in your unknown sample, you will identify the unknown materials by comparing the
unknown Rf values with that determined using your solvent system with the known
compounds provided to you.
Your report must contain sufficient information for your instructor to determine
that you identified all components in your unknown sample based upon your data
whether or not you actually identified the correct material.

Experiment 7
Column Chromatography Isolation of Chlorophyll from Spinach
In this experiment you will utilize column chromatographic techniques to isolate
chlorophyll and other pigments from spinach. The pigments are extracted from spinach
leaves using acetone as the extracting solvent. These pigments are separated using
column chromatography with alumina as the solid adsorbent.
Chlorophylls are green pigments that are the primary photoreceptor molecules of
plants. They absorb certain wavelengths of visible light that are converted into chemical
energy by the plants. The structure of chlorophyll-a is

O
O

Mg
N

OMe
N

O
OPhytyl

Important
You will be using hexane and acetone which are highly flammable organic
solvents. Do NOT have any open flames in the laboratory. These pigments are air and
light sensitive and you should work quickly. The column chromatographic process
takes about 15 minutes to perform. Once started you cannot stop until it is complete.
Be sure to have all materials available before you start so that you do not pause during
the process.
Experimental Procedure Extraction
Weigh about 1 g of fresh spinach leaves. Do use the stems or veins. Tear the
leaves into small pieces and place them in a mortar. Add 1 mL of cold acetone. Grind
the leaves with a pestle until the leaves have been broken into very small pieces. You
may need to add an additional 1 mL of acetone. Transfer the green colored acetone
solution using a Pasteur pipet into a small centrifuge tube and centrifuge the solution for
1 minute. Transfer the centrifuged solution to a clean test tube and add 2.0 mL of
hexane to the tube, cap, and shake vigorously. Add 2.0 mL of water and shake again,
venting occasionally. Re-centrifuge this mixture to break any emulsion that may have
formed. Remove the aqueous layer (bottom) using a Pasteur pipet. Pass the organic
solution through a Pasteur pipet containing about 0.5 1.0 g of anhydrous sodium
sulfate. Add an additional 0.5 mL of hexane to completely remove the organic pigment
solution. Evaporate the hexane by placing the test tube into a warm water bath.
Dissolve the residue in 0.5 mL of hexane.
Chromatography
Prepare a micro chromatographic column by placing a piece of cotton in the

bottom of a Pasteur pipet. Fill the pipet with 1.5 g of alumina. Tap the column with a
small piece of rubber tubing to ensure level packing. Clamp the column so that the
bottom of the column fits in the top of a test tube. You should see two bands of colored
materials pass through the column. The first band will be yellow or orange in color.
These are the carotenes. The second band will be green and consists of the
chlorophylls.
After the column is packed add approximately 3 mL of hexane to the alumina
carefully so that the surface is not disturbed. Allow the hexane to pass through the
column until the hexane just reaches the surface of the packed column. Carefully add
about of the green pigmented hexane solution to the top of the column and let the
solution run until it just reaches the surface of the alumina and add 1 mL of hexane to
the surface and let it run to the surface.
Add 4 mL of hexane and let it run through the column until you collect the yellow
carotene band. If the yellow band does not separate from the green pigment change
the next solvent to the more polar solvent (70% hexane: 30% acetone). Be sure to add
the next solvent when the last solvent reaches the surface of the alumina. Collect the
yellow band in a test tube labeled #2.
Add several mL of the next polar solvent (acetone) to the top of the column. If
the green band moves in this solvent continue to use acetone to collect the green
pigments in test tube labeled #3. If the green band does not move switch the solvent to
the more polar solvent 80% acetone 20% methanol. Collect the green band until no
more colored material passes out of the column.
Evaporate the solvents in each tube using a warm water bath. Stopper each test
tube and keep in the dark.
Thin Layer Chromatography
Add two drops of 70:30 hexane:acetone to each of the test tubes containing the
dried pigments and spot a silica gel tlc plate with the original extract and each of the two
pigments collected. Develop the tlc plate using 70:30 hexane:acetone. When fully
developed remove the plate, dry, and visualize immediately using uv light. You may
see several different pigments present. These include:
Carotenes yellow orange
Pheophytin grey and intense
Chlorophyll-a blue green
Chlorophyll-b - green
Xanthophylls yellow, could have 3 spots
Identify as many as you can. Calculate the Rf values for each spot present.

Experiment 8
Phase Transfer Catalysis Addition of Dichlorocarbene to Cyclohexene

Haloforms (HCX3) react with strong base to form dihalocarbene, a highly reactive
intermediate that is known to react with alkenes to form cyclopropanes as shown:

HCX3

base

X2C:

The general procedure used for this process requires t-butyl alkoxide as the base in tbutyl alcohol under anhydrous conditions. The reaction requires time, effort, and the
results are somewhat variable.
More recently a two-phase reaction has been developed that allows the alkene
and haloform to be in an organic phase while an aqueous solution of the base is used.
This reaction requires the presence of a catalyst to increase the speed of the reaction
because the primary reagents hydroxide and haloform are not in the same phase. This
catalyst is used to bring the reactive hydroxide ion into the organic phase and is known
as a phase transfer catalyst. Many reagents have been developed over the last few
years that fulfill the requirements for these catalysts, but the most common are
quarternary ammonium salts, such as benzyltriethylammonium chloride,
tetrabutylammonium bisulfate, cetyltrimethylammonium chloride. All of these materials
have a positive N atom and lots of carbon. These features allow the reagent to be
soluble in the organic phase while capable of carrying a hydroxide counter ion into the
organic phase.
In this experiment you will prepare 7,7-dichlorobicyclo[4.1.0]heptane from
cyclohexene.
CHCl3
Cl

ptc

Cl

NaOH (aq)
Experimental Procedure
Preweigh a 5 mL conical vial with cap. Charge this vial with 0.4 mL of cyclohexene.
Cap and reweigh to determine the mass of cyclohexene used. Add 1 mL of 50%
aqueous sodium hydroxide to the vial and 1 mL of chloroform to the vial. Add a
magnetic spin vane to the vial. Add 0.04 g of the phase transfer catalyst,
benzyltriethylammonium chloride to the vial and add an air condenser.
Place the vial in a hot water bath (40 oC) and stir vigorously for 1 hour. Remove the vial
from the bath and allow the reaction to cool to room temperature. Using a Pasteur pipet
transfer the reaction mixture to a centrifuge tube and add 1.5 mL of water and 1.0 mL of
methylene chloride. Shake the tube for 30 seconds. Allow the layers to separate.
Remove the methylene chloride layer with a Pasteur pipet and transfer it to a 5 mL
conical vial. Re-extract the aqueous phase using 1 mL of methylene chloride. Combine
the organic phases.

Transfer the combined organic extracts to a clean centrifuge tube. Add 1 mL of a

saturated aqueous sodium chloride solution and shake for 30 seconds. Transfer the
methylene chloride solution to a conical vial and dry it over anhydrous sodium sulfate.
Transfer the organic solution to a preweighed conical vial and evaporate the
solvent using a warm water bath. Report the mass and percent yield of the product
obtained.
Experiment 8
Relative Reactivities of Aromatic Compounds
In lecture we have seen that certain substituents on aromatic rings activate the
ring towards aromatic substitution reactions with electrophiles while other substituents
deactivate the ring towards these substitution reactions. In addition groups that activate
the ring also direct substitution toward the ortho and/or para positions on the ring, while
deactivating group direct substitution toward the meta ring position.

In this experiment you will examine the bromination of three substituted aromatic
compounds, acetanilide, aniline, and anisole.
O
H N

CH3

NH2

OMe

Each group in the laboratory will conduct the bromination on a different aromatic
compound and determine the structure of the product obtained from the melting point
data. The data for all groups will be shared so that each student can determine the
order of reactivity for these substituents.
The classical method of brominating an aromatic ring utilizes bromine and the
Lewis acid ferric bromide. Because of the activity of these substituents towards
aromatic substitution we will be brominating using a solution of bromine in hydrobromic
acid and acetic acid. You should be aware that bromine is a skin and respiratory tract
irritant and should not be used outside of a hood. Bromine will also oxidize jewelry.
Hydrobromic acid is a strong acid and may cause skin and/or eye irritation. Aniline is a
highly toxic compound and is a suspected teratogen. This experiment must be
conducted in the hoods at all times.

Melting Points of Relevant Aromatic Compounds

Compound
melting point (oC)
o-bromoacetanilide
99
p-bromoacetanilide
168
2,4-dibromoacetanilide
145
2,6-dibromoacetanilide
208
2,4,6-tribromoacetanilide
232

o-bromoaniline
p-bromoaniline
2,4-dibromoaniline
2,6-dibromoaniline
2,4,6-tribromoaniline

32
66
80
87
122

o-bromoanisole
p-bromoanisole
2,4-dibromoanisole
2,6-dibromoanisole
2,4,6-tribromoanisole

3
13
60
13
87

Experimental Procedure
To a preweighed 5 mL conical vial with a cap, add the given amount of one of the
following compounds:
0.09 g acetanilide
0.06 mL of aniline
0.07 mL of anisole
Reweigh the conical vial + cap + compound to determine the actual mass of the
aromatic compound chosen. Record the mass in your table. Add a spin vane and 0.5
mL of glacial acetic acid. Attach an air condenser and place the vial in a water bath at
room temperature. Stir until the aromatic compound is dissolved. While the compound
is stirring pack a drying tube loosely with glass wool to which you have added 0.5 mL of
a 1M sodium bisulfite solution. This will trap any bromine vapors given off during the
reaction.
Under the hood obtain 1.0 mL of bromine/hydrobromic acid solution. This
solution is transferred to the reaction vial through the air condenser using a Pasteur
pipet. Attach the drying tube to the top of the condenser and stir the mixture for 20
minutes.
Transfer the reaction mixture to a 10 mL Erlenmeyer flask containing 5 mL of
water and 0.5 mL of saturated sodium bisulfite solution. Stir this mixture with a stirring
rod until the bromine color disappears. If an oil forms continue stirring for several
minutes. Place the Erlenmeyer in an ice bath and continue to stir (or scratch the sides
of the flask) to induce crystallization. (the anisole may take up to 15 minutes to
crystallize). Vacuum filter the solid product using a Hrisch funnel rinsing with several 1
mL portions of cold water.

Recrystallization
Aniline:
transfer the solid product to a 10 mL Erlenmeyer flask and recrystallize
from 95% ethanol. Filter the crystals using a Hirsch funnel, let them dry in
your drawer for a week, obtain the melting point
Anisole:

transfer the product to a Craig tube and crystallize from hexane. Filter the
crystals using a Hirsch funnel, let them air dry in your drawer for a week,
obtain the melting point

Acetanilide: transfer the product to a Craig tube and crystallize from 95% ethanol.
Filter the crystals from a Hirsch funnel, let them air dry in your drawer for a
week, obtain the melting point
Report the identity of your brominated product based upon its melting point. Obtain the
melting points from your classmates and determine the order of reactivity for these
substituents. Calculate and report your yield and percent yield.