CH 222 Lab Manual-Fall 2017-BB-Final

CH 222 (Organic Chemistry I)
M I L W A U K E E S C H O O L OF E N G I N E E R I N G
1025 North Broadway Milwaukee, Wisconsin 53202-3109 Telephone (414) 277-7300
CH-222
Organic Chemistry-I
Department of Physics and Chemistry

Laboratory Manual
Revised Fall, 2017

Dr. Vipin Paliwal
Copyright 2017 by the Milwaukee School of Engineering

All Rights Reserved
1
TABLE OF CONTENTS
GENERAL INFORMATION...iii
CHEMISTRY LABORATORY SAFETY REQUIREMENTS....iv
DRAWER EQUIPMENT LIST.vi
DATA SHEETS..x
LABORATAORY NOTEBOOK..xi
INSTUCTIONS FOR LABORATORY DEVICES.... xiv
ETHICS......xviii
EXPERIMENTS
Experiment #1: Laboratory Techniques Wk. 1-Lab. Safety, liquid liquid extraction. Wk. 2-
melting point, Refluxing and TLC (Note: this is a two-week experiment)
Experiment #2: Laboratory Techniques Wk. 3- Simple distillation and estimation of boiling
point
Experiment #3: Nomenclature and Functional groups of Organic Compounds, Structure

representation (Wk. 4)
No lab in week 5
Experiment #4 Properties of Alcohols (Wk. 6)
Experiment #5: Synthesis of salicylic acid: Synthesis and start of recrystallization (Wk. 7)
Experiment #6: Synthesis of Aspirin: Synthesis and start of recrystallization (Wk. 8)
Experiment #7: Analysis of Salicylic acid and Aspirin (Wk. 9)
Additional Notes:
i) No laboratory in week 5
ii) Week 10: Catch-up week (no new experiment): Complete/Repeat any failed experiment at the
discretion of the instructor/Instructor planned activity
(iii) Most labs require Flow diagrams as pre-labs. Remember to make them after carefully
reading the procedure. This helps you come prepared.
2
Missed Lab Policy

CH-_______ Section#_______ Instructor:________________ Quarter:_____
CHEMISTRY LABORATORY DEPARTMENTAL ATTENDANCE POLICY
SIGN AND RETURN THIS FORM TO THE LABORATORY INSTRUCTOR
After the second missed lab period, a student will be dropped from the class before 8th week and
will fail the course after 8th week regardless of standing in other portions of the course.
A missed lab period is defined as a student not completing the designated experiment in the same
week it is assigned or an unexcused absence from the lab period. Excused absences include the
following:
1. Delayed registration (first week only)
2. Death in the family (documented or verified by Student Life Office)
3. Sickness to a point where the student is hospitalized (documented or verified by Student
Life Office)
4. Illness of a students immediate family member who is dependent upon the student for
support (documented by a physician or verified by the Student Life Office)
5. MSOE sanctioned activity including athletic event or academic competition (prior
arrangements required)
6. Road accident (documented or verified by Student Life Office)
7. Court Date (prior arrangements required)
8. Major religious holiday (prior arrangements required)
9. Unforeseen and unavoidable circumstance (prior arrangements or documented when
possible)
A student who misses -a scheduled lab period should contact their lab instructor by email or
phone within 24 hours of the missed lab period with the reason(s) for which the lab period was
missed. It is the responsibility of the student to follow-up this initial contact with other possible
lab sections (for the same course) that the student could attend that same week by checking the
timetable of classes at http://inside.msoe.edu/registrar or by looking at schedules posted on doors
of chemistry laboratory. Permission to attend another section must be granted by both the
students instructor and the instructor whose lab-section the student will attend for the missed lab
period. The students data sheets must be signed by the lab instructor for credit. The student will
follow his/her lab instructors policy for the lab report of a missed lab period.
___________________________________ _________________________________
Name-Print Last, First, Initial MSOE Student Number
___________________________________ ________________________________
Signature Date
3
Common Equipment List
beaker graduated cylinder scoopula
micropipettor; micropipet
Erlenmeyer flask extension clamp
water bottle; squirt bottle

funnel
clamp holder
gauze wire mesh

stir rod
Bunsen burner
evaporating dish
casserole dish
well plate
4
test tube brush Medicine dropper
Ignition tube (it is larger

and thicker walled than a
test tube)
test tubes test tube rack pipestem triangle
Bunsen burner lighter; striker watch glass

support ring
buret clamp
crucible tongs
ring stand
disposable pipet; Beral

pipet
buret
5
Instructions for commonly used Laboratory Devices
Measuring Mass
1. Never weigh chemicals directly on the balance pan; use a watch glass, beaker, or smooth
paper as a container. Clean up any spills.
2. If there is an apparent difficulty in operating the balance, consult an instructor. Do not
attempt any adjustments.
3. Do not remove analytical balances from their location.
4. Weigh volatile or corrosive samples in stoppered containers.
5. Do not weigh objects that are not at room temperature.
6. The precision of a top-loading balance is 0.0lg.
Measuring Volume
Medicine Droppers
A very rough, but often satisfactory, method for estimating volume is by counting drops
delivered from a medicine dropper. Generally, the approximation is 20 drops per milliliter.
Beakers and Flasks
The volume stamped with the trademark on beakers and flasks is only approximately correct.
Never measure volumes with a beaker or a flask.
Pipets
Pipets are calibrated in one of two ways: to deliver a given amount (marked TD) when allowed
to drain under gravity, or to contain a given amount between the limiting calibration marks
(marked TC). It is important for you to recognize which pipet type you have. For TD glassware,
the volume released is exactly the volume marked on the pipet. Some liquid will remain in the
pipet when deliver is complete. Do not try to shake this liquid out-it will make your delivered
volume inaccurate.
If a pipet is being used to measure an exact volume of a solution, the pipet should first be rinsed
with the solution. Gently touch connect the pipet pump to the top of the pipet, draw up a small
amount of the solution by rolling the wheel, then draw the rinse up and down the pipet, then
expel the rinse into a waste container by inserting the plunger. Larger pipets may be tipped on the
side and rotated after removing the bulb or pump, so the entire inner surface is rinsed.
To use a pipet, gently connect the pipet top to a pipet pump. Draw the liquid up, by rolling the
wheel until the liquid reaches the desired mark on the pipet. When making a reading, be sure to
have your eye at the same level as the meniscus in order to avoid problems due to parallax. The
meniscus is always read at curves center, regardless of whether it curves upward or downward.
Empty the pipet by inserting the plunger. Touch the tip to the side of the flask to remove the last
drop of liquid from the pipet.
6
Micropipettor
Always hold the micropipettor with the tip pointing/facing down when it contains liquid
and always draw liquid in/out slowly.
Selecting the Right Micropipettor
The range of the micropipettor is printed on its side (such as 200-1000 l). If you need to draw a
volume of 0.1 ml (100 l) you should use a micropipettor that has 100l within its range.
Setting the Volume
Set the delivery volume by rotating/turning the push button on the top of the pipette. To increase
the delivery volume, turn the push button counterclockwise. To decrease the delivery volume,
turn it clockwise. Make sure that the desired delivery volume clicks into place and that the digits
are completely visible in the display window located on the side of the micropipettor. Do not set
volumes outside the pipettes specified volume range. Using excess force to turn the push button
outside the range may jam the mechanism and eventually damage the pipette.
Push and release the push button slowly at all times. Never allow the push button to snap back.
Make sure that the tip is firmly attached to the tip cone.
To help eliminate the risk of contamination, each pipette is fitted with a tip ejector system. The
tip ejector system consists of a soft-touch tip ejector and specially designed gearing mechanism.
To release the tip, point the pipette at suitable waste receptacle and press the tip ejector with your
thumb.
Collect and dispense liquids
1. Fill and empty the tip 2-3 times with the solution that you will be pipetting.
2. Depress the push button to the first stop (just like the button in your digital camera-
where you push it halfway in to focus on the scene before clicking).
3. Dip the tip under the surface of the liquid in the reservoir to a depth of about 1 cm and
slowly release the push button. Withdraw the tip from the liquid touching it against the
edge of the reservoir to remove excess liquid. Deliver the liquid by gently depressing the
push button all the way to the second stop.
Graduated Cylinders
Graduated cylinders are perhaps the most available and versatile volume-measuring instruments
in the laboratory. However, burets are constructed so that it is possible to measure (and deliver)
volumes more accurately. For example, with a 50 ml buret, volume can be measured to within
0.0l ml, whereas with a 50 ml graduated cylinder, the value within which the volume can be
measured is closer to 0.l ml.
The meniscus is the curvature in the surface of a liquid contained in any narrow measuring tube,
caused in part by surface tension. In graduated cylinders or burets that are filled from the top it
is necessary to read the bottom of the meniscus (if there is a downward curvature) with the eye
horizontal to this surface. If the meniscus is not read at eye level, so that the front and rear parts
of the graduation mark nearest the meniscus appear to coincide, parallax error in the reading will
result.
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Titration
A titration involves the addition of a measurable amount of a standardized solution, the titrant,
into a pre-measured amount of a solution whose concentration is to be determined. A buret is
used to deliver and measure accurately the volume of the titrant.
Rinse the buret two or three times with distilled water, and then with an l0 ml portion of the
titrant. Clamp the buret in a vertical position. Rotate the stopcock so that the handle is in a
horizontal position, thus closing the stopcock. Pour 50-60 ml of titrant into a small beaker and
fill the buret from this beaker. Open the stopcock and allow a few milliliters of titrant to flow
through the tip. Close the stopcock.
Read the position of the liquid meniscus in the buret to the nearest 0.0l ml and record this as the
initial buret reading. A piece of paper held behind the meniscus will help you read the volume
correctly. The way that the buret is calibrated may seem backward. However, this makes it
easier to read differences in volume.
Accurately measure a known volume of the sample to be titrated in a graduated cylinder and
transfer it carefully to an Erlenmeyer flask. Add the required amount of indicator solution (if one
is to be used) and swirl the flask to mix the contents.
Titrate the flask contents by adding titrant from the buret to the flask; gently swirl the flask as
titrant is added. Fig. 2 shows how the stopcock should be manipulated to ensure accurate
delivery of titrant. The thumb and forefinger are wrapped around the handle to turn the
stopcock. You may add the titrant fairly rapidly at the beginning of the titration. However, as
the titration nears completion, you should add the titrant drop-wise, and swirl the flask after the
addition of each drop. You will know that the end point is near when the drop of titrant changes
color as it strikes the solution in the flask. When the endpoint is reached accurately read the
titrant meniscus to the nearest 0.0l ml and record this as the final buret reading.
During titrations one must remember:
1. The buret does not have to be filled exactly to the 0.00 ml mark as the initial volume for
each titration. As long as the liquid level is within the calibrated portion of the buret, its
volume can serve as the initial volume.
2. If the liquid level goes beyond the lowest calibrated point on the buret, the buret must be
refilled and a new sample titrated.
After you complete the required titrations, discard the solution remaining in the buret and rinse
with distilled water. Place the buret in an inverted position in the clamp.
Gravity Filtration
The simplest method for separating a liquid and a solid is by gravity filtration through paper. A
piece of filter paper is folded in half and then in half again. Open it out and tear off a small
corner of the outside fold. The tear is made in the corner of the paper to allow a close seal to be
made across the folded portion of the paper. Place the paper in a glass funnel, wetting the paper
slightly to keep it in place. Support the funnel in a ring with its stem touching the inside of a
beaker. Pour the mixture into the funnel along a stirring rod, as in the figure. Do not allow the
stirring rod to touch the paper. Never fill the filter paper more than two thirds full.
8
Spectrophotometer
The instruments will most likely already have been turned on and allowed to warm up at least 15
minutes. In general, the cuvettes should be wiped off on the outside with chem-wipes or other
soft absorbent paper, and inserted gently but firmly in the sample compartment.
Procedure
1. Set the required wavelength as described in the experiment.
2. Place a cuvette filled to the proper level with distilled water in the sample holder and set
the % transmittance to 100 % with the adjustment dial.
3. Remove the cuvette with distilled water and insert the cuvette with your sample.
4. Read the % transmittance directly.
9
pH Meter and Probe

The pH meter should be calibrated before use. A single point is all that is required, but two-point
or three-point calibrations are better.
1. Attach the probe to the meter and turn
on the meter.
2. Remove the probe from the storage
solution. The pH probe must always be
in a solution - either the storage solution
CAL for or a solution that you are measuring.
calibrate 3. Rinse the pH probe with distilled water
from a wash bottle into a waste beaker.
4. Place the pH probe into a standard such
as a pH 4 standard. Allow the pH probe
to equilibrate with the solution by
stirring it gently for 3 seconds and then
letting it sit for 30-60 seconds.
5. Hit Cal. The number will flash and
Hold/Enter then stop. Hit Hold/Enter. The pH
should match the standard within 0.05
pH units.
6. Repeat steps 3-5 for the other standards available.
7. If two of the values are off by more than 0.05 pH units, see your instructor for
assistance.
10
Experiment 1: Laboratory Techniques
This two-week experiment introduces you four important laboratory techniques

commonly used in an organic chemistry laboratory. Carefully READ the plan.
Week 1: (page 12-15)
(i) In the first part you will conduct liquid-liquid extraction of an organic
compound (benzoic acid) using a separatory funnel followed by
evaporation using rotovap.
Week 2: (page 16-29)

(ii) In the second part you will determine the melting point of benzoic
acid previously extracted in part I and a known pure & impure sample of
benzoic acid.
(iii) In the third part you will set up a refluxing apparatus and then extract
caffeine from tea leaves by the technique called refluxing. This is
followed by recovering caffeine using rotovap.
(iv) In the fourth part you will learn purification and characterization
technique known as Thin Layer Chromatography or TLC.
Pre-lab Week 1:
1. Watch the youtube clip by Dr. Mark Niemczyk on the apparatus called
Rotovap on the following link:
https://www.youtube.com/watch?v=FkBhsZy39Ck
2. Look up the density of the Methylene chloride online and report. Is this
organic solvent is more or less dense than water.
3. Research online and write a paragraph on the technique of liquid-liquid
extraction including the chemical principles involved.
4. What is the purpose of using a Rotovap in the procedure?
5. What is halogenated organic waste? Why it needs to be separated from other
organic waste?
6. Draw the structure of benzoic acid. Examine the structure and answer the
next question.
7. What are the molecular forces benzoic acid is expected to have? Which
solvent benzoic acid is expected to dissolve in?
Pre-lab Week 2: Complete assignment on page 17 and flow diagrams on page 26
Post lab questions: Answer questions on pages 27-29 and submit with report.
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(Week 1)
CHEMICALS & SUPPLIES for liquid-liquid extraction
Beakers Thermometer
Separatory funnel Erlenmeyer flask
Glass tubes Roto Vap
Graduated cylinders Transfer pipettes
Methylene chloride (Caution: Toxic & volatile)
Benzoic acid solution in water (0.20 g/100mL). Note: Should be kept warm (28-30 C) overnight.
Part -I. Liquid-liquid Extraction:

Introduction: Extraction is a technique used for separating a compound from a mixture. The
technique takes advantage of the different solubilities of a solute in a pair of immesible solvents.
Compounds can be selectively transported from one solvent phase to another.
Procedure: Wear gloves. Pour 50 ml of benzoic acid sample solution in a separatory

funnel (Note: the temperature of the solution should be slightly above the room
temperature @ about 300C so that bezoic acid remains dissolved). Add 10 ml
methylene chloride (Toxic! Handle carefully). Stopper the separatory funnel; hold the
stopper firmly in place with your index finger and middle finger as shown in Fig.1
below.
Fig. 1
12
Shake the separatory funnel in rocking motion for 30 sec. and then remove the vent
stopper (holding the funnel away from your face & others) to vent the funnel.
Repeat the shaking and venting procedure one more time and then let the
separatory funnel sit in a ring stand in an upright position without stopper until the
two layers separate.
When the two layers have separated, drain the methylene chloride layer (lower)
into a 150 ml Erlenmeyer flask. Transfer it into a 100 mL round bottom flask and
proceed to the rotovap apparatus for evaporation of the solvent. (Note: Only one
equipment is used for entire class. Please wait for your turn)
Note: Improper use can damage

this expensive equipment.
Follow instructions. If not sure
please ask.
Fig. 2 Rotovap Setup

Instructions for using the rotovap for evaporating an organic solvent::
IMPORTANT: It is expected that every student has watched the youtube video clip on rotovap before
using the apparatus. Follow the steps below to use the equipment.
Startup Procedure:
Rotovap instructions continued-
13
Slide the round bottom flask containing your sample onto the glass adapter and secure it
with a green clip.
Press the down arrow on the rotovap to lower the flask into the water bath so that the
liquid in the flask is just higher than level of the water in the bath.
Slowly turn the dial on the rotovap until the flask is spinning at 60 rpm.
Turn the yellow vacuum knob on the fume hood two full rotations (not more)
counterclockwise.
To start pulling vacuum on the sample, turn the glass valve on the condenser unit 90o to
close it.
Wait until the solvent has evaporated. You should see a layer of solid deposited in the
bottom of the flask.
Shutdown Procedure:
Press the up arrow on the rotovap to raise the flask out of the water bath.
Open the pressure valve on condenser unit by turning the glass valve 90o back to its
original position. This releases the vacuum on the sample.
Turn off the vacuum by using the yellow knob in the fume hood.
Stop the flask from spinning by turning the dial back to zero.
Remove the green clip and slide the round bottom flask off of the adapter.
Return to your station and proceed to next step with your sample.
Collect the extracted organic compound (benzoic acid) on to watch-glass by scraping

from the round bottom flask. Clean the round bottom flask completely with few drops of
methylene chloride and return it back in the kit.
Cover the watch glass with a plastic wrap, put your name and save it for determination of
its melting point using next week. Ask your instructor for storage.
Caution:
Do not fill the flask greater than half full.

Make sure bath temperature does not rise above 40 C.
Do not use round bottom flask with visible cracks. It can cause implosion.
Remember to clean the round bottom flask thoroughly.
Do not monopolize the rotovap. Other groups are waiting and need to complete the
experiment.
Rotovap area must be left CLEAN. Rotovap must be left in original position as you found
it.
Remove the round bottom flask with a firm grip. Dropping the flask in the waterbath will
create huge mess (your responsibility to clean up) making the equipment unusable to
other groups.
If water in the water bath is low, scummy contact your instructor.
Rotovap is an expensive and semi-fragile equipment. When using apply common sense
and follow instructions carefully.
14
Waste Disposal and Safety Notes (Ask your instructor if not sure).
Methylene chloride is toxic. Do not get it on your skin or inhale its
vapors. Wear gloves. Any methylene chloride or its solutions must be
poured into a specially labeled container for halogenated organic
waste.
Dispose any extra reagents and clean the glassware used. Beakers,
cylinders with reagents should not left behind. There will be group penalty for
leaving unclean glassware.
The water layer collected in the waste beaker is disposed in the aqueous
waste container.
This ends week 1
Important Reminder: Did you return ALL the equipment used, to its original
place, cleaned your station and closed student hood sash? You may leave the lab
now.
15
Week 2
Part II. Determination of Melting Point:
Introduction: Most organic compounds have well-defined melting points. It is the temperature at which
the solid coexists in equilibrium with the liquid at atmospheric pressure. The process of melting occurs
in a very narrow range of temperature (0.5-2oC). Impurities have a dramatic effect on the melting points
of organic compounds. You will determine the melting point of the benzoic acid you extracted in part I
and compare it with a known pure sample provided to you.
CHEMICALS & SUPPLIES for Melting Point determination

Melt-temp apparatus capillary tubes
Watch-glasses pestle and mortar
Long glass cylindrical tube
Solid benzoic acid samples (S1) pure (S2) benzoic acid you extracted
Procedure:
a) Filling a capillary with solid sample:
You will be provided with the sample of pure benzoic acid (S1). Make sure that the
sample is dry.
Solid samples can also be crushed into fine powders on a piece of paper using a
clean, dry spatula if needed.
Benzoic acid sample you extracted in part I (S2) can be directly crushed on the
watch glass.
Place few milligrams of crushed samples on a clean, dry, watch-glass. (Note: The 2
solid samples should not be mixed and should be on 2 separate watch-glasses).
Dip the open end of the capillary into the solid to lift the solid at the tip of the
capillary. (Ask your instructor to demonstrate how to fill a capillary).
Hold the capillary straight in a vertical position (sealed end at the bottom) and drop
it through a long open-ended cylindrical tube. This will help the sample fall to the
bottom of the capillary tube. A small amount of solid sample in the capillary tube
can be visualized in the melting point apparatus (~1-2mm in height is enough).
Repeat the process for the second sample.
b) Using MEL-TEMP capillary Melting Point Apparatus:

Place the sample (S1) filled capillary in the melting point apparatus and determine
the melting point of pure benzoic acid. (Ask your instructor to demonstrate). The
sample turns clear when it reaches its melting point. Record the melting point.
Repeat the process with extracted benzoic acid (S2) samples. Report the melting
points of each sample in the data sheet.
16
Post lab analysis:

(i) Report the melting points of the pure benzoic acid (S1) and extracted
benzoic acid (S2)
(ii) Find the literature value of melting point of benzoic acid online and
calculate % error in melting point of pure benzoic acid:
(iii) Based on the melting point obtained experimentally, and its

comparison with literature value, how pure is your sample?
(< 1% impurity = very pure, 1-5% =fairly pure, >5% impurity = very impure)
Part III: Refluxing

Pre-lab assignment for week 2: (i) Find an online video on the technique of refluxing, watch and
learn how to use it.
(ii) Define what is an open and closed system. Why it is necessary to keep top end of the condenser open
during refluxing?
(iii) Define what is chromatography. What is the principle of Thin layer chromatography. What is Rf
value. Provide the equation used for calculation of Rf value.
(iv)Describe the process of vacuum filtration. Why it is necessary to disconnect the side-arm flask
before turning off the vacuum?
(v)What is the literature value for % caffeine in tea leaves?
Purpose: You will be familiarized with Standard Taper Glassware (STG) from the
Organic equipment kit. This specialized glassware is delicate and should be
handled with care. In Part III you will set up a refluxing apparatus and then
extract tea leaves by the technique called refluxing.
CHEMICALS & SUPPLIES for Refluxing:

Tea leaves
Boiling Chips Buchner funnels
Condensers Rubber tubing (soft) for refluxing
Filter flasks Rubber tubing (thick & sturdy) for filtration
Filter papers STG (Orange equipment kit)
Glass funnels Gloves
Graduated cylinders Heating mantle & rheostat
Joint clips
Extraction Solvent: Methylene chloride/toluene (1:3)
17
Standard Taper Glassware (STG):
Visually identify the Taper glassware in the organic equipment kit provided and as shown in Fig.
3. Proceed to part III.
Figure 3 Standard Taper Glassware (STG)
Part III (Refluxing tea leaves)

Introduction:
Low boiling point solvents-when heated in an open container-evaporate very quickly. If a
container with a low boiling solvent is closed, it will explode when heated. Volatile solvents as a
result are heated under reflux. Refluxing simply means boiling a liquid while continually cooling
vapors and returning them to the flask as liquid. A condenser provides the means of cooling the
vapors. The design of the condenser allows continuous circulation of cold tap water in the outer
jacket of the condenser. Water should enter the condenser from bottom and leave from the top.
18
Procedure:
(i) Refluxing-
Assemble a refluxing unit as shown below in figure 4 using the STG
glassware from the kit.
19
This end of condenser remains

open
20
Figure 4
Place the round bottom flask on the heating mantle. Clamp the flask
firmly. Connect the heating mantle via rheostat to a power outlet (Ask
your instructor for rheostat setting).
Lift the condenser assembly and then add 50.00 ml of water and 1g of
tea leaves (record exact mass) into the round bottom flask. Add 6-7
boiling stones to the flask. Reset the condenser assembly back on the
round bottom flask. (Caution: Do not put tea leaves directly via
condenser because it can stick to the walls)
Attach rubber tubing to water inlet and outlet nozzles of the reflux
condenser. Attach water inlet (bottom) tube to water tap. Water outlet
(top) tubing should rest in a sink.
Open the water tap at a moderate rate so that the reflux condenser is
filled with circulating water at all times.
21
Before you proceed further, confirm the following:
o Condenser is vertical
o Heating mantle and round bottom flask are snug with each other
o Direction of water flow is correct (water in & water out)
o Water flow is constant and at moderate rate
Now show and discuss the set-up with your instructor before proceeding
further.
Heat the tea leaves mixture and boil it for 10 minutes. Begin measuring
the time when the mixture starts boiling. After 10 minutes remove the
heat first and let the solvent cool down (until you can touch the flask
with bare hands) with condenser still attached and the water still
circulating.
(ii) Vacuum Filtration:

Attach one end of a thick-walled rubber tube to the side arm of the filter
flask as shown in Fig: 5. The other end of the tube is connected to the
source of the vacuum in the laboratory (located in the student hood).
To vacuum outlet
Figure 5: Apparatus for vacuum filtration

22
Attach the rubber stopper-Buchner funnel assembly to filter flask.
Cover the flat bottom of the Bchner funnel with a Whatman circular
filter paper. Filter paper should size fit the Buchner funnel exactly and
should cover all the holes. Moisten the filter paper with few drops of
water and turn the vacuum on.
Take the reaction mixture from the round bottom flask and pour it into
the Buckner funnel slowly.
Turn on the vacuum and let it run for a 1 min. until filtration is
complete.
Note: ALWAYS DISCONNECT THE RUBBER TUBING FROM THE

VACUUM SOURCE BEFORE STOPPING THE VACUUM.
Record in your lab notebook the volume & color of filtrate.
Proceed to the extraction step with the filtrate and. discard tea leaves in
regular trash.
Extraction of Caffeine from the filtrate

Using the procedure of liquid-liquid extraction learned in the previous week,
extract the caffeine present in the filtrate
Wear gloves. Pour tea filtrate in a separatory funnel. Add 10 ml methylene
chloride/toluene extraction solvent (Toxic! Handle carefully).
Follow the steps of liquid-liquid extraction and extract caffeine in the
organic layer (methylene chloride/toluene)
Pour the organic layer (contains extracted caffeine) in a pre-weighed round
bottom flask (small size).
Using the rotovap apparatus evaporate the organic layer to recover the
extracted caffeine.
Weigh the flask and find the weight of caffeine recovered.
Post-lab Analysis:
23
Calculate the percent error by comparing caffeine recovered with the

reported value of caffeine in tea leaves.
24
Part IV: Thin Layer Chromatography (TLC):

Introduction: TLC is an important technique for the rapid separation and qualitative analysis
of small amounts of material. Every type of chromatographic analysis depends on the
distribution of the substances being separated between two phases, a mobile phase and a
stationary phase. The mobile phase is either a liquid or gas that carries the sample through
the stationary phase that can be liquid or solid. TLC uses glass, plastic, or metal plates
coated with thin layer of an adsorbant as a stationary phase. Silica gel (SiO xH O) and
2 2
Aluminum oxide (Al O ) are the most common ones.

2 3
CHEMICALS & SUPPLIES for TLC

Ethyl acetate Markers
TLC developing chamber Pencils
Caffeine sample (solid) TLC Plates (plastic sheets)
Transfer pipettes UV Box
Capillary tubes (open end) Solvent-Ethyl acetate:methanol 1:1(v/v)
Procedure:
a) Preparation of a developing chamber (Fig: 6):
Solvent used is 50:50 ethyl acetate:methanol and is provided. Add 3 ml of solvent system
to the developing chamber. (see fig. 6).
Safety Note: Ethyl acetate is toxic, an irritant, and very flammable. Avoid inhalation or
skin contact. Keep the developing chamber close at all times except when
inserting or removing a thin layer plate.
Close the chamber. The solvent should be about 0.5 cm deep in the bottom of the
chamber. Confirm it visually. Adjust the depth if necessary by adding or removing the
solvent. Set the chamber in student hood.
b) Spotting the Sample:

Caffeine: Obtain pre-made sample of caffeine solution. (Caution: Contains
chloroform which is toxic and a suspected carcinogen. Avoid inhalation or skin contact).
Preparation TLC Plate:

On the silica-side (non-shiny side) gently draw a line with a pencil at the long edge of a
2.5 x 6.5 cm silica gel thin-layer plate (Important: Plate is a plastic sheet coated with
silica. Use the silica chemical side for spotting) approximately 1 cm from the bottom
edge.
Spotting: Prepare a TLC plate by spotting caffeine sample.
25
Dip a clean applicator (caution: it is an open-ended capillary tube) into the caffeine
solution and apply one spot. Air-dry the spot for 30 seconds.
c) Development of TLC Plate:
Carefully put the TLC plate into the developing chamber, spot end down. (Careful: Avoid
touching plate to the filter paper liner).
Replace the cover on developing jar and place the jar in the student hood. Do not disturb
the developing chamber during the chromatography.
Allow the mobile phase to rise up the plate until it is about 1.0 cm from the top.
Remove the plate from the developing chamber with gloved hands.
Immediately mark the solvent front with a pencil line before the solvent begins to
evaporate.
Air-dry the plate for 30 seconds.

d) Visualization of Chromatogram:
Visualize the results of your caffeine chromatogram by shining ultraviolet (UV) light on
the TLC plate in UV box (Ask your instructor for help). A Dark spot indicates the presence of
caffeine. Make a circle around the dark spot with a pencil (mark lightly) while still
holding the plate under UV light.
Save the TLC plate. Tape the TLC plate in the results section of your lab report and label
them. (Caution: TLC plate must be taped and should not be submitted in any other way).
e) Clean Up and Waste disposal:

Any leftover ethyl acetate is disposed into the organic waste.
Solvent saturated filter paper or bad TLC plates are disposed into the solid waste
under the hood.
f) Post-lab Analysis: Calculate the Rf values of each sample (look-up online how to calculate)
and report in your lab report.
26
(Heating Mantle)
Figure 6: TLC Developing Chamber
27
Pre-Lab Week 2: Read the procedure and complete before coming to the lab. Submit
individually at the beginning of the lab. Attach initialed pre-lab with report as last page.
Flow Diagrams
Part II: Melting point:
Part III: Refluxing
Part IV: TLC
Your Name__________ Instructors Initials_____

28
Names (1) _____________ (2)_____________

QUESTIONS
Submit the post lab questions attached with lab report
1. (a) Describe what is chemical toxicity and toxicology.
(b) Define what is LD50 and LOD50 of a compound. What is LD50 of Aspirin in rats?
(c) (i) Why is proper disposal of hazardous waste important? (ii) Why it is important to dispose
off haloorganic compounds separately in a proper and safe manner?
2. While performing the extraction technique with water and methylene chloride (a) which
solvent formed the lower layer in the separatory funnel? (b) Explain in details why the two layers
of liquids separate.
29
3. (a) How is the melting point of a solid affected by the presence of impurities? (b) Explain its
chemical basis?
4. What was the purpose of washing the organic layer after extraction?
5. Explain why a reaction mixture heated in a refluxing apparatus for an extended period of time
does not lose solvent?
6. What is the purpose of condenser in the refluxing apparatus?
30
7. The TLC in the chamber with ethyl acetate solvent was used. (i) Explain why? (ii) suggest an
another alternate solvent that you can you replace it with in this experiment.
8. (i) Explain the principle behind why different samples travel different distances on the TLC
plate? (ii) What is the role of the solvent in separation of samples?
9. A silica gel TLC plate is developed in dichloromethane. (a) In what order (from top to bottom)
would you expect to find naphthalene, butyric acid, and phenyl acetate. (b) Provide an
explanation to your answer.
31
Experiment 2:
Laboratory Techniques-III
(Simple Distillation)
Purpose: You will be introduced to the technique of distillation for the separation
of two liquids from each other.
Pre-lab: Complete the flow diagram.
CHEMICALS & SUPPLIES:

Supplies: Organic Chemistry student STP glassware kit (orange kit)
Heating mantle
Stands
Clamps
Joint clips
Boiling stones
Chemicals: ethanol: water mixture
Introduction: Distillation is one of the oldest methods ever developed for the
purification of liquids. Briefly, distillation consists of heating a liquid to its boiling
point, condensing the vapors, and collecting the liquid condensate. The two most
common types of distillation are simple and fractional.
Procedure:
The apparatus for simple distillation is shown in Fig. 2.1. Set up the distillation
apparatus by following the steps described below-
1. Choose the small round bottom flask (100mL) from the STP glassware kit and
place a clamp on the neck of the flask. Attach the clamp to the stand. Using the
glass funnel pour 40 mL the liquid sample of ethanol-water mixture provided into
the flask. Add two boiling stones in the flask.
2. Attach the distillation head to the round-bottom flask and twist the joint to
achieve a tight seal. Make sure the bulb of the thermometer is below the level of
side arm. Attach rubber tubings to the outlets on the condenser jacket. Clamp the
condenser to the stand. Connect a vacuum adapter to the other end of the
condenser. Secure with joint clips.
Check your set-up: The distillation flask and distillation head need to be in a
completely vertical position and the condenser should be positioned with a
downward slant. Ask your professor to check your set-up.
32
3. Position an Erlenmeyer flask such that the outlet of the adapter is slightly inside
the mouth of the flask. The flask serves as the collection vessel.
4. Gently push the thermometer through rubber sleeve on the thermometer adapter
(caution ! be careful not to break the thermometer). Adjust the position of the
thermometer to align the top of the thermometer with the bottom of the side arm on
the distillation head (see figure below).
Note: 1.The bulb of the

thermometer must be below the
side arm.
2. Confirm the water in and out
flows are connected correctly and
tubing does not kink.
Fig. 2.1
7. Turn the water on. Check to ensure that water flows in at the bottom and out at
the top.
8. Place a heating mantle under the distillation flask (caution: mantles matching
size of round bottom flask are used). Ensure the heating mantle and flask are snug
tight. Set the Rheostat at 87 oC and start heating the flask.
9. Collect 10 mL of the condensate in the collection flask. Record the temperature

at which first drops of condensate begin to appear. Record the temperature at
which the last drop of condensate is collected. Continue distillation until the
temperature reaches 90 oC, then shut off the heat source. Let the flask cool down
to room temperature. (Important Note: It is essential to stop the distillation by
removing the heat source before the distillation flask reaches dryness. By
33
leaving a small amount of liquid in the flask you will prevent the flask from
overheating and will also avoid frustrating cleaning).
10. Measure the volume of the condensate. Measure the volume of liquid left over
in the flask (Note: These are also referred as fractions).
Data collection, observations and Analysis:

Data:
a) Volume of the condensate collected:
b) Volume of liquid left in the flask:
c) Density Test:
1. Pipette 1mL distilled water in a plastic weigh boat and record its weight on a pan balance.
2. Pipette 1mL ethanol in a plastic weigh boat and record its weight on a pan balance.
3. Repeat the process with each fraction. Record the weight.

4. Calculate the density of water, ethanol and each of the fractions.
d) Solubility Test:
1. Pipette 1 mL of distilled water, ethanol and each of the fractions in separate test tubes.
2. Add a pinch of sugar (tip of spatula) to each of the test tubes.
3. Shake the test tubes for 20 to 30 seconds.
4. Make observations for solubility of sugar in each sample.
Observations:
(1) Condensate:
c) Density test.
d) Solubility test.
(2) Liquid left in the flask:

c) Density test.
d) Solubility test..
Analysis:
a) Calculate the average boiling point of the condensate. Find literature value
online and calculate % error and report.
34
b) Calculate the percent of ethanol and water in the original mixture?
35
Name _____________ Sec._____________ Expt. #______
Questions
1. The entire bulb of the thermometer must be below the level of side arm in order
to obtain an accurate distillation temperature. Why is this important?
2. Why is cold water circulated through the condenser from the bottom rather than
from the top?
3. Describe what are azeotropic mixtures? Provide an explanation why are

azeotropic mixtures formed?
36
4. Pure ethyl alcohol boils at 78.4o C. Was the average boiling point of the
condensate in your experiment different? If yes, provide an explanation.
5. In theory, what is the composition of the liquid collected as condensate? What is

the composition of the liquid that remained in the distillation flask?
6. The total volume of liquid obtained (condensate plus liquid left in flask) is not
equal to the volume that you started in the distillation flask. What are the possible
sources of losses in this procedure?
37
Flow Diagram: (pre-lab assignment, individual)
Instructors Initials______________
38
EXPERIMENT # 3:
Nomenclature and Functional Groups of Organic Compounds, Structure determination

Materials Required:
1. Laptop computer with downloaded ChemSketch freeware (ACD/ChemSketch Freeware,
Advanced Chemistry Development, Inc., Canada).
2. Molymod Molecular Model kit (provided).
3. Organic Chemistry Textbook (bring with you in lab).
Pre- lab assignment:

1. Using the attached form, for every compound on list A:
a) Name the compound.
b) Predict their three-dimensional shape of a compound using VSEPR
method.
c) Predict polarity of the compounds.
2. Download and install ChemSketch Freeware from

http://www.acdlabs.com/download/chemsketch/ according to the instructions
found on website.
3. Read the instructions Creating and analyzing chemical structure in
ChemSketch program found at the end of this experiment. This is important for
the success of this lab. Sign the note I have read the required instructions and can
use the software. ____________(signature).
Introduction:
Functional groups: defined as parts of molecular structures, composed of atom or atoms and
exhibiting a characteristic chemical behavior, are features allowing us to classify compounds
according to their properties, including reactivity. This fact allows us to study the general
reactivity of compounds and predict the behavior of new compounds. Functional groups also
provide the basis for naming organic compounds.
In understanding the chemical properties of a compound, the first step is to understand its
three-dimensional structure. One of the best methods to do so is to utilize the physical models of
the molecules. With developing technology, other tools, including visualization software, also
had been created. Specific programs offer a good way to draw chemical structures and
mechanisms of reaction, visualize three-dimensional molecules, but also to calculate theoretical
properties of a givens structure or to name a compound according to IUPAC guidelines. You will
be introduced to such a program and is available as freeware online. Practicing drawing chemical
structures is educational and fun.
39
40
Lab Activities:
1. Analyze the compounds in the list A. Generate their two-dimensional and three-
dimensional structures using ChemSketch software. (See instructions Creating
and analyzing a chemical structure in ChemSketch program.) Perform 3D
optimization of the structures and generate 3D views of the molecules.
2. Build physical models of your molecules using Molymod kit and compare them
with computer visualizations and your predictions from pre-lab assignment.
3. Using ChemSketch software, perform following activities and answer the following
questions for the compounds from list A.
a) Using the program, generate the names for each of the structures.
b) (Optional: At the discretion of the instructor) In 3D viewer measure:
i. For compound 1: distance between atoms C1-C2 and H-C1.
ii. For compounds 1, 2, 3: bond angle between bonds C1, C2 and C3.
iii. For compound 5: Torsion angle between planes defined by H on N atom,
N atom, adjacent C atom and C1 atom.
4. Using the software, draw the structure of hydrocarbon consisting of 10 carbon

atoms. It should have eight single, one double and one triple bond. Answer the
following queries:
a. Should it be called an alkane, alkene or alkyne?
b. Explain your answer. Generate the name for this structure.
c. Using the software, calculate molecular formula, formula weight,
composition and index of refraction for this compound.
Post lab Questions:

1. Analyze the compounds from the list B. Identify their functional groups.
2. The following compound names are incorrect. Draw their structures and provide the
correct IUPAC names.
a) 2,2-dimethyl-6-ethylheptane
b) cis-1,5-dimethylcyclohexane
3. For the set of compounds shown below, (i) order them according to their relative
boiling points using your knowledge about polarity and intermolecular interactions.
Explain your predictions in details.
41
(ii) Next, check online and provide the literature values of their boiling points. To do
so, you will need to name your compounds first. Were your predictions correct?
O CH3
H3C CH
a) CH3
CH2 CH3
HO CH
b)
CH3
HO CH2 OH
c)
CH2 CH2
CH2 CH3
H3C CH
d)
CH3
42
List A (Organic Compounds)
Compound Name 3D shape Polar/Non-

polar
CH2 CH3
1 H3C
2
CH2
4
1 3
CH CH3
2 H3C
2
CH
4
1 3
3 H3C1 C
2
C
3
CH3
4
CH2 O
4 H3C
2
CH
3 1
H2C CH NH2
3' 2'
5 C CH2
1'
4' CH
5'
43
List B (Functional Groups)
C
H2C CH
H3C CH CH
1. O CH2
CH3 C NH
HO
CH2 C HC CH2 CH2
OH C O
CH3
2. HO
HS
C CH
HC CH O C CH
CH C C O
CH2 HC
3. NH2
44
IMPORTANT: Read these instructions before coming to lab. Sign the pre-lab note (pg. 36)
Creating and analyzing chemical structure in ChemSketch program.
1. Open a new file. Name and save your file.

More than one structure can be included. A file can consist of multiple pages. The
page flipper is at the bottom of the screen. [1]
2. Select Structure mode [2]
3. Click a desired element symbol to begin drawing. You can change it clicking at a
different element symbol. Click anyplace within the drawing area to create the
structure. Clicking on the drawn atom will add a subsequent atom to the structure.
Clicking on the bond changes it from single to double to triple to single.
4. To stop drawing, select the select/move tool. [3] Molecules can be moved and
rotated with use of select/rotate/resize and 3D rotation tools.
5. Double clicking on the atom brings up formatting window. [4]
6. In that window, change show carbons to all. Uncheck auto box for size
calculation. Change atom symbol size to 10 and bond length to 10 mm. Name this
style CH-222 and save. This will be the style used throughout all the activities. Set
it as a default.
7. Clean structure tool changes bond length and atom sized to default and generally
cleans up the drawing. [5]
8. To generate the name for the structure, select the structure, and go to tools [6]
generate name for structure.
9. To calculate selected properties of your compound, in structure mode select the

compound, go to tools calculate and then select the desired property
(Molecular formula and Formula weight).
45
10. 3D optimization tool [7] changes a planar drawing into three-dimensional structure to
prepare it for 3D viewer. Do not remove hydrogens for optimization. 3D optimized
structures can be saved as internal ChemSketch files, pictures, animations, or MDL
Molfiles (V3000). Files of *.mol type are commonly recognized by chemistry
software.
11. The structures can be copied and pasted.
12. To see your molecule in 3D viewer go to ACD/Labs 3D-viewer. [8] The screen
will change to 3Dviewer. Change back to ChemSketch (bottom of the screen), select
your molecule and click copy to 3D at the bottom of the screen.
13. In 3D viewer you can change the appearance of your molecule (View-styles) [9]
and measure different properties (Tools should be visible on the top toolbar. [10] If
not, add needed tools to the toolbar by clicking on the small arrow on the toolbar.[11])
14. To measure the bond length select Bond length tool [10] from the toolbar. When
you select two atoms, the function return distance between them.
15. To measure the bond angle, select angle tool. After selecting three adjacent atoms,
the function returns the angle between bonds.
16. To measure the torsion angle between two planes defined by four adjacent atoms,
select torsion angle tool and then four adjacent atoms. The function returns the
value of the torsion angle.
46
6 8
3 7
4
3
-methylheptane, octane, and 2,2,4-trimethylpentane.
10
11
47
Experiment 4:
Properties of Alcohols
Purpose: In this experiment you will (i) understand the comparative solubility of alcohols (ii) perform
qualitative tests for the identification of alcohols.
Pre-lab: Complete the flow diagram.
Introduction: Organic compounds which contain the functional group -OH, the hydroxyl group, are
called alcohols. Alcohols are important commercially and include use as solvents, drugs, and
disinfectants. The most widely used alcohols are methanol or methyl alcohol, CH3OH, ethanol or ethyl
alcohol, CH3CH2OH, and 2-propanol or isopropyl alcohol, (CH3)2CHOH. Methyl alcohol is found in
automotive products such as antifreeze and "dry gas." Ethyl alcohol is used as a solvent for drugs and
chemicals, but is more popularly known for its effects as an alcoholic beverage. Isopropyl alcohol, also
known as "rubbing alcohol," is an antiseptic.
Classification: Alcohols are be classified as primary (1), secondary (2), or tertiary (3):
H R' R'
R C OH R C OH R C OH
H H R"
RCH 2OH RR'CHOH RR'R"COH

1 alcohol 2 alcohol 3 alcohol
Phenols bear a structural resemblance to alcohols in that the hydroxyl group is present.
However, since the -OH group is bonded directly to a carbon that is part of an aromatic ring, the
chemistry is quite different from that of alcohols. Phenols are more acidic than alcohols; concentrated
solutions of the compound phenol are quite toxic and can cause severe skin burns. Phenol derivatives
are found in medicines; for example, Thymol is used to kill fungi and hookworms.
OH CH3 OH
OH OH
phenol thymol resorcinol
In this experiment, you will examine the physical and chemical properties of representative
alcohols and phenol. You will be able to compare the differences in chemical behavior between these
compounds.
48
Chemicals and Supplies:
Methanol Ethanol
Butanol Hexanol
Octanol Phenol
1-butanol 2-propanol
2-methyl-2-propanol Resorcinol
Hexane
Lucas reagent Chromic acid reagent
Ferric Chloride I2-KI reagent (iodoform)
10% NaOH Test tubes (10x130 mm)
Water bath made from a 600 mL beaker on a hotplate (1 per team)
Part I: Solubility of Alcohols: The ability of alcohols to participate in intermolecular hydrogen

bonding enhances their solubility in water. You will compare the solubility of alcohols with
different number of carbons that are present.
Procedure:
1. Label two sets of 6 test-tubes (10x130 mm) for the following samples of alcohols provided to you:
1. Methanol
2. Ethanol
3. Butanol
4. Hexanol
5. Octanol
6. Phenol
2. Set-up the test tubes in a stand, number them 1-6 and to each test tube add 1 ml of alcohol sample.
3. To 1st set of alcohol samples, add 1 ml of distilled water.
4. To 2nd set of alcohol samples, add 1 ml of hexane.
5. Close the test tubes with a cork (or a gloved finger) and gently mix the solutions in each test tube.
6. Let the test tubes stand for 1 min.
7. Observe the solubilities of various alcohols in water and hexane. Record your qualitative
observations in the data sheet provided in the manual.
8. Dispose the samples in the organic waste container in the hood.
49
Part II: Chemical Tests For Alcohols
1. Lucas Test. This test is used to distinguish between primary, secondary and tertiary alcohols.
Lucas reagent is a solution of zinc chloride, ZnCl2, in concentrated HCl. Upon addition of this
reagent a tertiary alcohol reacts rapidly and immediately gives an insoluble white layer. A
secondary alcohol reacts slowly and after heating slightly gives the white layer within 10 min. A
primary alcohol does not react. Any formation of a heterogeneous phase or appearance of an
emulsion is a positive test. The test is also time and heat dependent.
CH3CH2-OH + HCl + ZnCl2 ---> no reaction

1o alcohol
(CH3)2CH-OH + HCl + ZnCl2 ---> (CH3)2CH-Cl + H2O (10 min., heat)

2o alcohol insoluble white layer
(CH3)C-OH + HCl + ZnCl2 ---> (CH3)3C-Cl + H2O (immediate)

3o alcohol insoluble white layer
2. Chromic acid (oxidation) test. This test is able to distinguish primary and secondary alcohols
from tertiary alcohols. Using chromic acid, also known as Bordwell-Wellman reagent, primary
alcohols are oxidized to aldehydes and subsequently to carboxylic acids; secondary alcohols are
oxidized to ketones; tertiary alcohols are not oxidized. In the oxidation, the orange color of the
chromic acid changes to a blue-green solution. Phenols are oxidized to nondescript brown tarry
masses.
3 CH3CH2OH + 4 H2CrO4 + 6 H2SO4 ---> 3 CH3COOH + 2 Cr2(SO4)3 + 13 H2O

1o alcohol orange carboxylic acid blue-green
3 (CH3)2CHOH + 2 H2CrO4 + 3 H2SO4 ---> 3 (CH3)2C=O + Cr2(SO4)3 + 8 H2O

2o alcohol orange ketone blue-green
(CH3)3COH + H2CrO4 + H2SO4 ---> No Reaction No change

3o alcohol orange remains orange
3. Iodoform test. This test is more specific than the previous two tests. Only ethyl alcohol and 2 o
alcohols with a methyl group directly attached to the carbon bearing the hydroxyl group react.
These alcohols react with iodine in aqueous sodium hydroxide to give the yellow precipitate
iodoform.
50
OH O
R C CH3 + 4 I2 + 6 NaOH R C O- Na + + 5 NaI + 5 H2O + HCI 3
H
iodoform
yellow ppt
Phenols also react under these conditions. With phenol, the yellow precipitate tri-iodophenol forms.
I
OH OH
+ 3 I2 + 3 HI
I I
4. Acidity of phenols. Phenol is also called carbolic acid. Phenol is a weak acid and will react with
base; thus phenols readily dissolve in base solutions. In general, organic compounds that bear a
charge are soluble in water. In contrast, alcohols are not acidic.
OH O- Na+
+ NaOH + H2 O
5. Ferric chloride test. Addition of aqueous ferric chloride to a phenol gives a colored solution.
Depending on the structure of the phenol, the color can vary from green to purple. This color
change can be used to differentiate alcohols from phenols.
OH OFeCl2
+ FeCl3 + HCl
Procedure:
1. Set up hot water bath at 600C by filling a 250-mL beaker 1/3-full of water. Obtain the following four
alcohol samples: 1-butanol, 2-propanol, 2-methyl-2-propanol and resorcinol. Perform the 5 tests as
described below. In each of the tests, remember to include a test tube for water control (tube # 5). Also,
have an empty beaker at your station to collect waste.
2. Lucas test: In 4 separate test tubes add 5 drops each of the four samples. Add 1 mL of the Lucas
reagent (please do not be wasteful with this reagent). Mix well by swirling the mixture in the test tube.
Allow each test tube to stand for five minutes. Look carefully for any cloudiness that may develop
during this time period. If there is no cloudiness after 10 minutes, warm the test tubes that are clear for
15 minutes in a 60oC water bath. Record your observations in the table.
3. Chromic acid test: In 4 separate test tubes add 5 drops each of the four alcohol samples. Add 10
drops of acetone and 2 drops of the chromic acid (Caution: Very corrosive. Use gloves)). Mix the
contents by swirling the tubes. Note the initial color of each solution. Place the test tubes in a warm
water bath (~60C) for 5 min. Again, note the color of each solution. The loss of the orange color and
51
the formation of a blue-green color is a positive test. (If only a small amount of green appears this could
be due to a trace amount of isopropyl alcohol found in the acetone and should be considered negative).
Record your observations in the table.
4. Iodoform test: In 4 separate test tubes add 5 drops each of the four alcohol samples. Add 10 drops of
10% NaOH to each. Tap the test tube with your finger to mix. Warm the mixture in a ~60C water bath
and add 20 drops of I2-KI (Iodoform) test reagent dropwise, with shaking. (Note: If no color change
occurs 10 more drops. Stop adding more reagent). Remove the test tubes from the water bath, let cool
and look for a light yellow precipitate. Record your observations in the table.
5. Ferric Chloride test: In 4 separate test tubes add 5 drops each of the four alcohol samples. Add 2
drops of ferric chloride solution to each. Note any color changes in your solution. Record your
observations in the table.
Waste Disposal and Precautions (If not sure ask your instructor): Dispose all waste in appropriate
organic waste container. Caution: Chromic acid and its salts are classified as suspected carcinogens.
Avoid touching with bare hands. If any of the above materials spill on skin, immediately rinse
thoroughly with water and then wash with soap and water.
52
Submit the data sheet before leaving the laboratory (discretion of instructor).
Name _____________ Sec._____________ Expt. #______
DATA SHEET:
Solubility Table:
Completely soluble = XXX
Partially soluble = XX
Sparingly soluble = X
Not soluble = NS
Methanol Ethanol Butanol Hexanol Octanol Phenol

Water
Hexane
Chemical Test Table Template:
# 1 2 5
Test Primary Secondary Tertiary
Lucas
Chromic
acid
Iodoform
Ferric
chloride
53
# 3 4
Test Phenol Water control Any comments
Lucas
Chromic
acid
Iodoform
Ferric
chloride
Note: Data sheet tables are for illustration purpose only. You may want to create your own table
(in landscape mode) for the report.
54
Post-lab Questions (submit with lab report)

1. Provide a logical explanation for the different solubilites of alcohols you observed in water and in
hexane.
2. Draw the structures of 1-hexanol and 2-methyl-2-hexanol. Using two tests performed in this
experiment indicate how you could distinguish between 1-hexanol and 2-methyl-2-hexanol? Provide
an explanation.
3. Primary alcohols and secondary alcohols can be oxidized with chromic acid, but tertiary alcohols
cannot. How do the structural differences between the alcohols account for the observed reactions?
Draw structures to support your answer.
55
Flow Diagrams: (pre-lab assignment, individual)
Part I: (solubility)
Part II: (chemical tests)
Instructors Initials______________
56
EXPERIMENT # 5:
SYNTHESIS OF SALICYLIC ACID
CHEMICALS & SUPPLIES:

Supplies:
Tub ice-water bath (50-50 ice-water)
Boiling stones
Buchner funnel set up in hood
Erlenmeyer flasks 125 ml
Whatman filter paper (small circles)
Heating mantle & Rheostat
Reflux condenser (from orange kit)
Round bottom flask, small (from orange kit)
Metal spatula
Disposable plastic transfer pipettes
Weighing boats
Thermometers (C)
Hot plates
Waste container in hood for organic solvents
Chemicals:
Ice
Methyl salicylate (Liquid)
NaOH solid
Sodium bicarbonate
Sulfuric acid (3 M)
Introductory Note:
Salicylic acid is a white, crystalline compound. It finds use in ointments and plasters for the
removal of warts from the skin. Methyl salicylate is a derivative of salicylic acid and is added as
a flavoring agent in candies because of its fragrant minty smell.
Purpose: The purpose of this experiment is to introduce you to organic synthesis. Once the
chemical structure of a drug is established, it is economically superior to synthesize a drug
compared to extracting from natural sources. Pharmaceutical companies synthesize billions of
dollars of drugs via organic synthesis.
Background Theory:
Methyl salicylate has two functional groups that will show their functionality in this experiment;
one is the ester group and other is the phenol group.
The phenol group of methyl salicylate is a weak acid that rapidly reacts with NaOH, a strong
base, to form a sodium salt.
57
The ester group of methyl salicylate is converted into carboxylic acid by base promoted
hydrolysis. Hydrolysis is the splitting apart of the ester group by a molecule of water. The base
that promotes hydrolysis is NaOH. The product of hydrolysis will yield one molecule each of
alcohol and carboxylic acid. The carboxylic acid-in the presence of strong basic reaction
mixture-reacts and changes to carboxylate anion and as a result the hydrolysis reaction becomes
irreversible. Since the salicylic acid, produced in the reaction is insoluble in cold water it
precipitates out as solid. Alcohol produced in the reaction is soluble in water and is removed in
the filtration step along with the filtrate.
PROCEDURE
SYNTHESIS OF CRUDE SALICYLIC ACID:
Pour 25 ml of water into a 100 ml round-bottom flask.

Add 4.6 gm (0.12 mol) of sodium hydroxide, (NaOH) to the flask (Caution: NaOH is
corrosive and causes burns. Wear gloves. Use spatula and weighing boats to handle it
and avoid contact with skin, eyes, and clothing. Important: Close tightly the NaOH
bottle immediately after use).
Swirl the flask gently until the NaOH is dissolved. Stir the mixture gently if needed.
Measure 2.0 ml (2.3 g, 0.015 mol) of methyl salicylate Caution: (toxic and an irritant.
Avoid contact with skin, eyes, and clothing) with a transfer pipette and add to the round
bottom flask that contains NaOH solution. You should see a white solid form quickly.
Add 4-5 boiling stones, attach reflux condenser to the round bottom flask, turn water on.
Show the refluxing set up to your instructor (to make sure your set is correct, consult
refluxing fig. in expt. # 1 for set up)
Heat the mixture at reflux for 15 minutes on a heating mantle The white solid that formed
earlier should start dissolving as the mixture is warmed.
After 15 minutes of reflux heating remove the heating mantle and let the mixture cool to
room temperature (you should be able to touch with bare hands).
Carefully add 5 ml of 3 M sulfuric acid solution in 0.5 ml portions to the room
temperature solution in the round bottom flask (Be very careful. Sulfuric acid is
corrosive and causes burns. Avoid contact with skin, eyes or clothing).
Swirl after each addition.
Continue adding 1.0 ml increments of 3M sulfuric acid until a heavy white precipitate of
salicylic acid forms and remains when the mixture is well stirred; then add one 1.0 ml
portion of sulfuric acid more to complete the precipitation (Be patient: You may need a
total of 10-20 ml of the acid).
Cool the round bottom flask containing salicylic acid in the tub ice bath.
Vacuum filter the salicylic acid precipitate using a Buchner funnel and filter flask set up
in hood.
Save approximately 50mg (about a pinch, weighing not required) of crude salicylic acid
for melting point determination.
58
RECRYSTALLIZATION OF SALICYLIC ACID:
Label two 125-ml Erlenmeyer flasks as # 1 and # 2.

Add 60 ml water in flask # 1.
Heat the water until almost boiling (about 85 to 90 C).
Transfer the crude solid salicylic acid from the buchner funnel into flask # 2.
Carefully pour approximately 20 ml of hot water from flask # 1 into flask # 2.
Add 2-4 boiling stones into flask # 2 and heat the flask to boiling.
Keeping record of the estimated amount of water continue adding approximately 5 ml
portions of hot water into flask # 2 until the solid has completely dissolved, allowing a
little time after each addition for the dissolution process to occur (may have to heat @ 70
C & stir for complete dissolution)
When dissolution is complete, add 8-10 ml of excess hot water.
Leave the flask on the lab bench to cool down to room temperature. Notice the
appearance of crystals as the solution starts cooling.
Place the flask in ice-water bath for 5 minutes.
Vacuum filter the crystals again using Buchner funnel and filter flask assembly.
Continue to pull air through the crystals for 3 to 4 minutes to facilitate drying.
Transfer the crystals on a watch glass using the metal spatula. Cover the watchglass
lightly with plastic wrap, write your name on sticky note and save for analysis in the
instructor provided bin.

ANALYSIS: Save the crude and re-crystalized salicylic acid on two separate watch glasses and determine the
melting point in experiment 7.
Waste Disposal (If not sure ask your instructor)
Neutralize any excess acid in the filtrate from the reaction mixture with solid NaHCO3.
Test it with pH paper. Bring the pH between 5-12 and then discard solution in sink.
Salicylic acid and filter paper are discarded in trash.
59
Pre-lab:
Flow Diagrams: (pre-lab assignment, individual)
I. Synthesis:
II. Re-crystallization:
Instructors Initial_______
60
Post-lab Questions:
1) Why was the crude salicylic acid re-crystallized?
2) Why was water used as re-crystallization solvent for salicylic acid?

Can any other solvent be used?
3) Propose two methods that can be used to assess the purity of crude salicylic acid?
61
4) Draw the structural formula, IUPAC name and physical properties (color, mp, solubilities) of
salicylic acid.
5) Suppose the material that you are re-crystallizing fails to precipitate out of the cold
solvent. What would you do to recover the material from the solution?
62
Q6) Translate the following statements into a chemical equation.

Report all the compounds in their full structural formulas in the chemical equations.
a) Methyl Salicylate + 2 Sodium Hydroxide gives methanol + water + sodium
derivative salt of methyl salicylate.
b) Methanol + water + sodium derivative salt of methyl salicylate gives salicylic
acid + sodium sulfate by the addition of excess of sulfuric acid.
7) The melting point of the re-crystallized salicylic acid has given a range of two or three
degrees, with upper limit of the range slightly below the (real) literature value of the
melting point of salicylic acid, 159 C.
What can you do to the product to obtain a melting point closer to the literature value?
63
Experiment # 6:
Synthesis & recrystallization of Aspirin (Acetyl salicylic acid)
Pre-lab: Flow diagram and balanced chemical equation.

Chemicals & Supplies:
Supplies:
Tub ice-water bath (50:50 ice-water)
600 mL Beaker for water bath
Buchner funnel filteration set up
Erlenmeyer flasks (125 ml)
Filter flask
Whatman Filter paper #1 (small circles)
Glass rod
Hot Plate
Funnels
Metal spatula
Thermometer (C), one per team
Disposable plastic transfer pipettes
Weighing boats
Chemicals:
Ice
Acetic anhydride (liquid)
Ethanol (ethyl alcohol)
Phosphoric acid (85 %)
Salicylic acid (solid)
Sodium Bicarbonate
Introduction:
Aspirin is one of those few synthetic organic compounds that have a gigantically wide spread
medicinal use. In United States alone 30 million lbs of aspirin are used every year. Aspirin is
used against headaches, discomforts of colds, minor pains and arthritis. Although the extract
from the willow tree leaves and bark was used as an analgesic (pain reliever), and antipyretic
(fever reducer) for centuries, it was only in 1800s that the active ingredient of the Willow and
Poplar bark was discovered to be salicylic acid. It was found that the synthetic preparation-in
huge amounts-of this active ingredient was cheap but salicylic acid because of its acidic nature
was a severe irritant to the stomach lining. A German chemist, Flex Hoffmann, in 1893
synthesized an acetyl derivative of salicylic acid. The synthesis was a breakthrough because the
acetyl derivative had the same medicinal properties as salicylic acid without the high degree of
irritation to the mucous membranes of stomach. Aspirin tablets include a binder such as starch to
hold the tablet in a stable shape. The usual 5-grain (an apothecary unit of mass) aspirin contains
0.325 g of acetylsalicylate acid. Mostly ingested aspirin passes through the stomach unchanged
64
because stomachs contents are acidic but under alkaline conditions in the intestines, aspirin
forms sodium acetylsalicylate, which is absorbed through the intestinal wall. Aspirin has been
cited as a possible contributor to the Reyes syndrome, which can lead to death. Aspirin also
seems to interfere with blood clotting. This anti-coagulant property of aspirin limits its use for
the patients anticipating surgery but renders it effective in reducing heart attacks and strokes by
preventing blood clots.
BACKGROUND:
Aspirin can be synthesized by acetylating salicylic acid in a process called esterification.

Esterification is the reaction of carboxyl (-COOH) group and an alcohol (-OH) group. The result
of the reaction is the formation of carboxylate ester group. The source of the OH group is the
phenolic OH attached to the ring of salicylic acid. The acetyl group comes from the acetic
anhydride and the reaction is catalyzed by phosphoric acid.
PROCEDURE
Esterification of Saliccylic acid:
Prepare a water bath using a 600 mL beaker. Make sure that the temperature of the water
bath does not exceed 45-50 C.
Prepare an ice-water (50:50) bath. (a common pre-made bath may be provided)
Weigh 1.0 g of salicylic acid that was synthesized in the last weeks experiment. (Note: If
your previous experiment failed, obtain a commercial sample of salicylic acid from the
instructor. Make sure that the salicylic acid you use is completely dry. (Caution:
Remember to save the rest of salicylic acid for experiment # 7)
Place the weighed salicylic acid in a 125 ml Erlenmeyer flask.
Under the hood, measure 2.0 ml of acetic anhydride with a transfer pipette and add to the
Erlenmeyer flask containing salicylic acid.
Add 5 drops of 85% phosphoric acid and ro/tate the flask to mix the chemicals
thoroughly. Allow it to stand in the student hood for 10 minutes. The flask may become
warm.
Heat the flask for 5 min in the water bath that you prepared earlier. Swirl the flask to mix.
Make sure the temperature of the water bath is 45-50C. Transfer flask to ice-water bath.
Chill the mixture in the ice-water (50:50) bath. Using a clean stirring rod scratch the
inside walls of the flask.
A semi-crystalline paste will start forming.
Add 10 ml cold water and about 6 g ice into the flask.
Stir the mixture to break up the pasty solid.
When the ice has melted, collect the crystals by vacuum filtration using Buchner funnel
and vacuum aspirator. This is crude Aspirin.
Important: Set aside about 10 mg (a pinch) of crude Aspirin for the melting point
determination (next week).
65
Re-crystallization of Crude Aspirin:
Stir rest of the crude aspirin crystals with 2.0 ml of ethanol in a 125 ml Erlenmeyer flask.
The crystals will dissolve at room temperature. (If they do not dissolve warm the mixture
briefly on a hot plate set at the lowest setting).
Cool the solution at room temperature for 5 minutes and then cool the solution in ice-
water bath for 5 minutes to complete the crystallization process. Consult your instructor if
crystallization does not occur.
Collect the product by vacuum filtration using a Buchner funnel and filter flask assembly.
Wash the product with 1 ml of ice-cold water and remove as much liquid as possible
through vacuum suction by pulling air for 2 minutes.
Allow the crystals to dry on the watch glass until next week. This is recrystallized
Aspirin.
Analysis: Save the crude and recrystallized Aspirin on two separate labeled watch glasses and
determine the melting point in experiment 7. Ask your instructor for proper storage.
Waste Disposal (if not sure ask your instructor)
Discard the waste in the aqueous waste container. (Note to technician: Neutralize the waste with
sodium bicarbonate).
Note: If the recrystallization fails for some reason, do not worry. Your instructor will
provide you a sample of pure Aspirin for experiment 7.
66
Pre-lab: (individual). Write the balanced chemical equation (using structural formulas)
including names of reactants and products for Aspirin synthesis. [Note: Do not copy and paste
from internet].
Flow Diagram:
67
Instructors Initials______
68
Post Lab Questions: (SUBMIT WITH THE LAB REPORT)
1) What is the principle on which mixed solvent re-crystallization method is based

upon?
2) List 5 characteristics of a good analgesic medicine.
69
3) Find and draw the molecular and structural formula of Acetylsalicylic acid.
4) Why did the procedure called for scratching the inside surface of the flask during
esterification?
70
5) List one active ingredient for each of the following:

Tylenol, and Motrin.
Give names and draw structural formulae and circle to indicate the functional
groups.
6) (i) How do the active ingredients of Aspirin different from that of Tylenol, Ibuprofen
and Motrin? Explain using your knowledge about functional groups. (ii) Why are
buffers added to some commercial aspirin products?
71
EXPERIMENT # 7:
ANALYSIS OF SALICYLIC ACID & ASPIRIN
Introduction: Part I: In this experiment, you will determine the melting point of the crude
and recrystallized salicylic acid and crude and recrystallized Aspirin. You will also determine
the melting point of commercial salicylic acid and Aspirin for comparison.
Part II: You will analyze your Aspirin samples using thin layer chromatography.
Part I: Determination of Melting Point:

Chemicals & Supplies:
Your samples from experiment # 5 and 6
Commercial samples of salicylic acid and Aspirin
Mel Temp apparatus
Capillary tubes
Thermometers (range up to 200oC)
PROCEDURE:
Weigh the dried samples of crude and recrystallized salicylic acid and Aspirin from
experiment 5 and 6. Report the weights in your lab-report.
For melting point determination, fill six capillary tubes with the following samples:
S1: crude salicylic acid (your sample)
S2: recrystallized salicylic acid (your sample)
S3: commercial salicylic acid (provided)
---------------------------------------------------------------
S4: crude aspirin (your sample)
S5: recrystallized aspirin (your sample)
S6: commercial aspirin (provided)
Determine the melting point of each sample and report in your lab-report (refer
experiment #1 for detailed procedure for the determination of melting point).
DISPOSAL: Discard all the capillary tubes in the broken glass container. Discard any
leftover samples of salicylic acid and aspirin in designated waste containers.
ANALYSIS:
1. Find the theoretical and percent yields of crude and recrystalized samples of salicylic acid
and aspirin
2. Find the literature values online for melting points for salicylic acid and aspirin and report
3. Using literature values determine the percent error in melting points for each of the six
samples.
72
Part II: Thin Layer Chromatorgraphy (TLC):c

You learned the technique of TLC in Experiment # 1. You will apply the technique for the
analysis of Aspirin. (Note: analysis of salicylic acid not required).
Chemicals & Supplies: TLC chamber, pencils, filter paper, TLC plates (pre-cut), UV box,
capillary tubes.
Your Aspirin samples S4, S5 & S6, 50:50 mixture of ethanol and dichloromethane, Ethyl
ethanoate
PROCEDURE:
On a TLC plate draw a line with a pencil (no pen) across about 1 cm from the bottom.
Mark 3 equally spaced points on this line. (caution: Do not touch the surface of the
TLC plate with your fingers)
Weigh about 0.05 gram of your crude aspirin, recrystallized aspirin and the
commercial sample in three separate eppendorf tubes and label them as S1, S2 S3.
Add 1 mL of solvent (50:50 mixture of ethanol and dichloromethane) in each test
tube and dissolve the samples.
Add 4-5 ml of ethyl ethanoate solvent to the developing chamber. Solvent should
about 4 to 5 mm deep in the bottom of the chamber.
Use capillary tubes to spot each of your three samples onto the plate. Spot should not
be bigger than 1-2 mm in diameter. Allow the spots to dry.
After the spots are dry, place the TLC plate in the developing chamber and it close
with the lid.
Allow TLC to develop until solvent front is about 0.5 cm from the top of the plate.
Remove the plate and quickly mark the position of the solvent front. Allow the plate
to dry.
Visualize the chromatogram under short wavelength UV light and circle the spots
with a pencil.
Take a picture with your smart phone and use it in the results section of your report.
Make sure you label the picture.
ANALYSIS: Calculate the Rf values of each sample and report in the analysis section of the
report.
DISPOSAL: Discard all the capillary tubes in the broken glass container. Discard any
leftover samples of aspirin in designated waste containers. Discard 50:50 solvent mixture in
halogenated waste. Discard ethyl ethanoate in organic waste container.
73
Post-lab Questions:
1. Write a paragraph discussing the results including explanation for quantittive errors
observed, for the melting point determination of salicylic acid and aspirin.
2. A student conducts TLC for crude aspirin and measures the solvent height on a TLC plate
as 11.5 cm. Three spots were observed. Spot A was measured at a height of 4.7 cm, spot B
at 2.3 cm, and spot C at 8.2. Assuming that Rf value for aspirin is 0.71, which spot is
aspirin? (Show complete work in support youre your answer).
74
Pre-lab: (individual)
Flow Diagram
Part I: Melting Point
Part II: Thin Layer Chromatography (TLC)
Instructors Initial_______
75

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CH 222 (Organic Chemistry I)

Department of Physics and Chemistry

Revised Fall, 2017

Copyright 2017 by the Milwaukee School of Engineering

CHEMISTRY LABORATORY SAFETY REQUIREMENTS....iv

DRAWER EQUIPMENT LIST.vi

INSTUCTIONS FOR LABORATORY DEVICES.... xiv

Experiment #3: Nomenclature and Functional groups of Organic Compounds, Structure

Experiment #4 Properties of Alcohols (Wk. 6)

Experiment #6: Synthesis of Aspirin: Synthesis and start of recrystallization (Wk. 8)

Experiment #7: Analysis of Salicylic acid and Aspirin (Wk. 9)

Missed Lab Policy

Common Equipment List

beaker graduated cylinder scoopula

Erlenmeyer flask extension clamp

water bottle; squirt bottle

gauze wire mesh

test tube brush Medicine dropper

Ignition tube (it is larger

test tubes test tube rack pipestem triangle

Bunsen burner lighter; striker watch glass

disposable pipet; Beral

Instructions for commonly used Laboratory Devices

pH Meter and Probe

Experiment 1: Laboratory Techniques

This two-week experiment introduces you four important laboratory techniques

Week 2: (page 16-29)

Pre-lab Week 2: Complete assignment on page 17 and flow diagrams on page 26

Part -I. Liquid-liquid Extraction:

Procedure: Wear gloves. Pour 50 ml of benzoic acid sample solution in a separatory

Note: Improper use can damage

Fig. 2 Rotovap Setup

Collect the extracted organic compound (benzoic acid) on to watch-glass by scraping

Do not fill the flask greater than half full.

This ends week 1

CHEMICALS & SUPPLIES for Melting Point determination

b) Using MEL-TEMP capillary Melting Point Apparatus:

Post lab analysis:

(iii) Based on the melting point obtained experimentally, and its

Part III: Refluxing

CHEMICALS & SUPPLIES for Refluxing:

Standard Taper Glassware (STG):

Figure 3 Standard Taper Glassware (STG)

Part III (Refluxing tea leaves)

This end of condenser remains

Before you proceed further, confirm the following:

(ii) Vacuum Filtration:

Figure 5: Apparatus for vacuum filtration

Attach the rubber stopper-Buchner funnel assembly to filter flask.

Note: ALWAYS DISCONNECT THE RUBBER TUBING FROM THE

Record in your lab notebook the volume & color of filtrate.

Extraction of Caffeine from the filtrate

Calculate the percent error by comparing caffeine recovered with the

Part IV: Thin Layer Chromatography (TLC):

Aluminum oxide (Al O ) are the most common ones.

CHEMICALS & SUPPLIES for TLC

b) Spotting the Sample:

Preparation TLC Plate:

c) Development of TLC Plate:

Air-dry the plate for 30 seconds.

e) Clean Up and Waste disposal:

Figure 6: TLC Developing Chamber

Part III: Refluxing

Part IV: TLC

Your Name______ Instructors Initials_

Names (1) _ (2)_

Name _______ Sec._ Expt. #