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CH-222
Organic Chemistry-I
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CH 222 (Organic Chemistry I)
TABLE OF CONTENTS
GENERAL INFORMATION...iii
DATA SHEETS..x
LABORATAORY NOTEBOOK..xi
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
No lab in week 5
Experiment #5: Synthesis of salicylic acid: Synthesis and start of recrystallization (Wk. 7)
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.
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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
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CH 222 (Organic Chemistry I)
micropipettor; micropipet
evaporating dish
casserole dish
well plate
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CH 222 (Organic Chemistry I)
buret clamp
crucible tongs
ring stand
buret
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CH 222 (Organic Chemistry I)
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.
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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.
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CH 222 (Organic Chemistry I)
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.
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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?
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.
Fig. 1
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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)
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-
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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.
Caution:
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.
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.
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CH 222 (Organic Chemistry I)
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.
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.
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CH 222 (Organic Chemistry I)
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.
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CH 222 (Organic Chemistry I)
Visually identify the Taper glassware in the organic equipment kit provided and as shown in Fig.
3. Proceed to part III.
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Procedure:
(i) Refluxing-
Assemble a refluxing unit as shown below in figure 4 using the STG
glassware from the kit.
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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.
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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.
To vacuum outlet
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.
Proceed to the extraction step with the filtrate and. discard tea leaves in
regular trash.
Post-lab Analysis:
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CH 222 (Organic Chemistry I)
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.
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CH 222 (Organic Chemistry I)
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.
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.
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).
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.
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(Heating Mantle)
CH 222 (Organic Chemistry I)
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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:
(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.
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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?
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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.
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CH 222 (Organic Chemistry I)
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.
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.
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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).
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.
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CH 222 (Organic Chemistry I)
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).
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.
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.
Analysis:
a) Calculate the average boiling point of the condensate. Find literature value
online and calculate % error and report.
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CH 222 (Organic Chemistry I)
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CH 222 (Organic Chemistry I)
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?
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CH 222 (Organic Chemistry I)
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.
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?
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Instructors Initials______________
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CH 222 (Organic Chemistry I)
EXPERIMENT # 3:
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.
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CH 222 (Organic Chemistry I)
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CH 222 (Organic Chemistry I)
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.
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.
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CH 222 (Organic Chemistry I)
(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
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CH 222 (Organic Chemistry I)
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'
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CH 222 (Organic Chemistry I)
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
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CH 222 (Organic Chemistry I)
IMPORTANT: Read these instructions before coming to lab. Sign the pre-lab note (pg. 36)
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.
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.
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CH 222 (Organic Chemistry I)
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.
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.
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CH 222 (Organic Chemistry I)
6 8
3 7
4
3
10
11
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CH 222 (Organic Chemistry I)
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"
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
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.
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CH 222 (Organic Chemistry I)
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)
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.
5. Close the test tubes with a cork (or a gloved finger) and gently mix the solutions in each test tube.
7. Observe the solubilities of various alcohols in water and hexane. Record your qualitative
observations in the data sheet provided in the manual.
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CH 222 (Organic Chemistry I)
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.
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. 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.
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CH 222 (Organic Chemistry I)
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
CH 222 (Organic Chemistry I)
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.
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CH 222 (Organic Chemistry I)
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
Hexane
# 1 2 5
Lucas
Chromic
acid
Iodoform
Ferric
chloride
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CH 222 (Organic Chemistry I)
# 3 4
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
CH 222 (Organic Chemistry I)
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.
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CH 222 (Organic Chemistry I)
Part I: (solubility)
Instructors Initials______________
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CH 222 (Organic Chemistry I)
EXPERIMENT # 5:
SYNTHESIS OF SALICYLIC ACID
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.
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CH 222 (Organic Chemistry I)
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
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CH 222 (Organic Chemistry I)
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
CH 222 (Organic Chemistry I)
Pre-lab:
Flow Diagrams: (pre-lab assignment, individual)
I. Synthesis:
II. Re-crystallization:
Instructors Initial_______
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CH 222 (Organic Chemistry I)
Post-lab Questions:
1) Why was the crude salicylic acid re-crystallized?
3) Propose two methods that can be used to assess the purity of crude salicylic acid?
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CH 222 (Organic Chemistry I)
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?
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CH 222 (Organic Chemistry I)
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
CH 222 (Organic Chemistry I)
Experiment # 6:
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
CH 222 (Organic Chemistry I)
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:
PROCEDURE
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
CH 222 (Organic Chemistry I)
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.
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
CH 222 (Organic Chemistry I)
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
CH 222 (Organic Chemistry I)
Instructors Initials______
68
CH 222 (Organic Chemistry I)
69
CH 222 (Organic Chemistry I)
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
CH 222 (Organic Chemistry I)
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?
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CH 222 (Organic Chemistry I)
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.
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.
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CH 222 (Organic Chemistry I)
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.
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CH 222 (Organic Chemistry I)
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).
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CH 222 (Organic Chemistry I)
Pre-lab: (individual)
Flow Diagram
Instructors Initial_______
75