CH 203 Lab Manual SS - 2012

Montgomery College - Takoma Park/Silver Spring Campus
CH 203 Organic Chemistry I
MELTING POINT DETERMINATION
Introduction
The melting point (MP) of a pure substance is defined as the temperature at which
the solid and the liquid phases of the substance coexist in equilibrium. If heat is applied
to a solid substance, the temperature of the substance will not increase beyond its melting
point until all the solid has melted. If heat is removed from the substance, the
temperature will not drop until all the liquid has changed back to the solid state. In
practice, the melting point of a substance is recorded as a temperature range from when
the sample begins to melt to when the entire sample has melted. An extremely pure
sample will usually have a very tight melting point range that is ≤ 3C.
If a broad MP range is observed (≥3C), it could be due one or more of the

following reasons: (1) the presence of impurities, (2) poor heat transfer, (3) non-uniform
temperature distribution. Non-uniform temperature distribution typically occurs when
not all the solid particles are at the same temperature because the crystals are large or the
sample size is too big.
The most common cause of a broad Mp range, however, is sample impurities. In
addition to the range broadening, impurities also causes the temperature at which the
sample starts melting to be lower than expected. We can take advantage of these facts to
determine whether or not a substance is pure. In addition, the identity of an unknown can
be determined by comparing the MP of an unknown substance with known substances
and doing a mixed melting point test. For example, let’s say that pure substance A has a
published MP of 150-151C. An unknown X gave MP range is 149-151C. It can be
determined whether or not unknown X is substance A by simply taking the melting point
of the mixture of the two (mixed MP determination). This is accomplished by preparing a
sample consisting of about a 1:1 ratio of X and A and taking the melting point. If A and
X are identical, then the mixture results in a pure sample and the MP should be identical
to that of X. If A and X are different, then the mixed MP would be lower and have a
broader range indicating an impure sample.
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In today’s experiment, the Mp apparatus will be used to determine the MP for a
pure substance first to familiarize you with the apparatus and the technique. Then the
identity of an unknown will be determined by using the MP and mixed MP techniques.
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Experimental Procedure:
Part I: Melting Point Determination of benzoic acid.

1. Obtain two melting-point capillary tubes and add about 2-4 mm of benzoic acid.
2. Insert one capillary tube in the melting point apparatus.
3. Turn on the heat so that the rate at which the temperature increases about 10-15C
every minute.
4. Watch the sample through the magnifying glass and record (trial 1 on the data sheet)
the temperatures when the sample begins melting (T1) and when the entire sample has
melted (T2).
5. Turn off the heat source and allow the temperature to decrease below 90C.
6. Insert the second capillary tube containing 2-4 mm benzoic acid into the apparatus.
7. Turn the heat source back on and this time adjust the heating rate so that the
temperature increases slower (~2-4C per minute) to get a more accurate MP.
8. Record the trial 2 MP range (T1 and T2) for benzoic acid.
Part II: Determination of the Identity of an Unknown Sample.
A. MP of the unknown.
1. Obtain an unknown sample and record the sample number.
2. Using the procedure above, repeat steps 1-8 for the unknown sample.
3. Record the MP range for the unknown on the data sheet.
B. Mixed MP
1. Select two compounds from Table 1 below that have a MP very similar to the unknown.
2. Obtain the vials containing pure samples of the two compounds you selected.
3. Using these compounds, prepare a 1:1 mixture with the unknown (a small spatula
tip of each) making sure mixture very homogeneous.
4. Determine the MP of these mixtures by repeating steps 6–8 from part I above.
5. Identify the unknown.
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Table 1: Melting Points of Possible Unknown Compounds
Compound MP (C) Compound MP (C)
benzoic acid 122-124 urea 132-135
acetanilide 113-115 salicylic acid 158-161
succinimide 123-125 triphenylmethanol 163-165
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Data Sheet
Name________________________________ Date________________
Partner(s) name(s):______________________________________________
Melting Point Range of Benzoic Acid

Benzoic Acid T1 T2
Trial 1
Trial 2
Melting Point Range of Unknown

Unknown #_________ T1 T2
Trial 1
Trial 2
Selected Compounds with Closest Melting Points

Name Melting Point (from table)
Compound 1
Compound 2
Mixed Melting Points

Mixture 1:1 T1 T2
Compound 1:Unknown
Compound 2:Unknown
Identity of Unknown
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Post Lab Questions
1. Explain why the melting point depresses and broadens when a sample is impure.
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THIN LAYER CHROMATOGRAPHY (TLC)
Introduction
Chromatography is a separation technique commonly used in organic chemistry to
separate the components of a mixture (purification) or identify the number of components
in a mixture. The two main types of chromatography are gas chromatography and liquid
chromatography. Within these categories there are several special techniques used to
enhance the separation capability of the system based on the nature of the analyte (i.e.
molecules in the mixture) one is working with. The two main parts of a chromatography
system are a mobile phase and a stationary phase. The gas/liquid part of the type of
chromatography refers to the nature of the mobile phase being used. The type of
chromatography that is introduced in today’s lab is thin layer chromatography (TLC) and
is in the liquid chromatography category.
As mentioned above, chromatography consists of both a mobile phase and a
stationary phase. Thin Layer Chromatography (TLC) uses some solvent (developing
liquid) as the mobile phase and a solid stationary phase. Becauase TLC takes advantage
of the polarity of the molecules in the analyte for separation, the choice of solvent
(developing liquid) for TLC depends on the nature of the analyte and thus can vary
greatly from sample to sample. Many times, mixtures of miscible1 solvents with different
polarities must be used to acquire the desired separation. The stationary phase can be
relatively nonpolar, neutral or polar. The most common stationary phase (and the one
that will be used in today’s lab) is silica gel (silicon dioxide, SiO2) which is polar. For
TLC, the SiO2 is deposited as a thin layer on a surface such as glass, aluminum or plastic.
The type of TLC plate people choose to use usually depends on ease of use or price.
Glass is usually the cheapest and aluminum the most expensive. Plastic and aluminum are
most user friendly and plastic TLC plates will be used in today’s lab for that reason.
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A miscible mixture is when two liquids do not separate at any ratio.
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TLC works by taking advantage of the polarities of the compounds in the mixture
one is trying to separate. A very small amount of sample is spotted on the stationary
phase using a capillary pipette. (The layer of stationary phase is very thin, 0.1-1.0 mm
thick, so only a very small amount of material should be used when performing TLC.)
The TLC plate is then placed in a developing chamber containing the mobile phase
(solvent of choice). The solvent will then travel up the plate via capillary action and
depending on the interaction of the compound with the stationary phase and/or the
solvent, the component will move up the plate as well. The distance the component
travels up the plate is described by its retention factor (Rf value). Every compound has a
specific Rf value for a specified solvent and is calculated by dividing the distance the
compound traveled up the plate by the total distance the solvent traveled (eqn 1)
(therefore all Rf values are ≤ 1).
After the TLC plate is developed to the desired solvent height, the compounds
must be visualized. Since most organic molecules are inherently colorless, the silica gel
is prepared with a fluorescent indicator. The compounds can then be visualized by
looking at the TLC plate under a UV lamp. The silica gel will appear fluorescent green
and where the compound is located, a dark spot will be observed because the compound
is blocking the silica gel from the UV light.
Since the stationary phase on the TLC plates for this experiment is very polar, a
more polar molecule will be more strongly attracted to the stationary phase than the
mobile phase and will travel much slower than a less polar molecule. If compounds have
significantly different polarities, they will have different interactions with the solvent and
stationary phase, and move at different rates up the TLC plate (i.e. have different R f
values).
If you are working with known compounds, usually the Rf values are recorded in
the literature for a specific solvent system. However, the solvent/solvent mixture in the
literature may not match exactly to the one you want to use. This situation can be
rectified by running the TLC of the known compounds in the desired solvent.
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In today’s experiment, four different developing solvents (mobile phases) will be
studied to determine the effect of polarity of the solvent on the mobility of the
compounds. In addition, a mixture of unknown components will be separated using TLC.
Using pure samples of the possible components (and their respective Rf values), the
identity of the components in the mixture will be determined.
There are three possible components in each of the unknown mixtures:
acetaminophen, acetylsalicylic acid, and mandelic acid. The unknown mixtures may
contain one, two, or all three of the known components. The mobile phase is prepared
using different ratios of ethyl acetate and hexanes. This ultimately will change the
polarity of each solvent significantly. The six ratios of 0/100, 20/80, 40/60, 60/40, 80/20,
and 100/0 hexanes to ethyl acetate will be studied. These solvent mixtures will be
prepared prior to the lab and will be provided.
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Experimental Procedure (work in groups of 4 students):
1. Obtain an unknown and record its number in the data sheet.
2. Obtain four jars (developing chambers) and place a piece of large filter paper
sideways inside.
3. Label each jar as solvent 2, solvent 3, solvent 4, and solvent 5 (instructor will
demonstrate using solvent 1 and 6). Under the hood, add approximately 10 mL of
solvent 2 to the jar labeled solvent 2. Repeat, adding solvent 3 to the jar labeled
solvent 3 and solvent 4 to 4 and solvent 5 to 5. Close the lid tightly on each jar and
shake lightly to saturate the filter paper.
Developing Solvents
Solvent 1: 0% hexanes – 100% ethyl acetate
4. Obtain four TLC plates and a ruler from the instructor’s table.
5. Using a pencil (no ink pens), gently draw a straight line across the TLC plate (on the
silica gel side) ~ 1 cm from the bottom (I, below). Then draw four hash marks on the
line and label the ‘lanes’ A, B, C, and X (II below). A will represent the
acetaminophen solution, B will represent the acetyl salicylic acid solution, C will
represent the mandelic acid solution, and X will represent the unknown.
6. Using a capillary tube (remember to use a different capillary tube for each solution),
place a small spot of the acetaminophen solution at the cross mark above A, a small
spot of the acetylsalicylic acid solution above B, a small spot of the mandelic acid
solution above C, and a small spot of the unknown mixture solution above X.
[one student from each group of 4 should prepare a TLC plate]
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7. Allow the spotted TLC plates to dry for 2-3 minutes.
8. Place one TLC plate in each of the jars labeled solvent 2 through solvent 5 and
replace the lid.
9. After the solvent front has traveled up the plate to about 1 to 2 cm from the top,
remove the plate from the jar and draw a line with pencil on the plate representing the
solvent front (see below).
10. Allow the plates dry for one or two minutes. Then, using the UV-lamp, visualize the
spots and draw a circle around any or all of the spots in each lane with a pencil. Draw
pictures of the plates on the data sheet.
a. After running the TLC, empty the jars in the waste container.
11. Using the ruler, measure the precise distance the solvent front traveled (from the line
where the solutions were spotted) and record the distance on the data sheet. Record
this all four TLC plates.
12. Now, measure the distance the compounds A, B, C, and X traveled (use the center of
the circled spot) from the original line where they were spotted. Again, record these
values on the data sheet for each of the four TLC plates.
13. Use the data sheet to calculate and record the Rf values for all compounds (including
the one(s) in the unknown mixture).
14. Use the Rf data and TLC plate pictures to determine the component(s) in the
unknown mixture.
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Data Sheet
Name__________________________________________________ Date________________
Partner(s) name(s):_________________________________________________________________
Distance traveled from the origin (cm) Rf

Percentage hexanes / ethyl acetate Percentage hexanes / ethyl acetate
0/100 20/80 40/60 60/40 80/20 100/0 0/100 20/80 40/60 60/40 80/20 100/0
Solvent front NA NA NA NA NA NA
acetaminophen (A)
acetyl salicylic acid (B)
mandelic acid (C)
Unknown Spot 1
Solution
Spot 2
(X)
(if present)
Spot 3
(#_____ )
(if present)
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TLC Plate Data
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Post Lab Questions
1. Based on the TLC results, which of the known compounds was the most polar?
2. Based on the TLC results, which of the known compounds was the least polar?
3. When observing the TLC plates, were all the spots nice small circles? If no, provide and
explanation as to why this might be the case.
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Pre Lab Questions
1. Complete the following table:
Compound Acetaminophen Acetyl salicylic acid Mandelic acid
Structure
Solubility in hexanes
Solubility in ethyl
acetate
2. Using the following diagram of a TLC plate, answer the following questions:
a) Which compound is more polar if the stationary phase is silica gel?
b) True or False: If the solvent mixture was made less polar, the compounds
would move farther.
c) Use a ruler and calculate the Rf value for compounds A and B (show work).
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STEREOCHEMISTRY
Introduction
During your education in chemistry, the term isomer has been mentioned many times.
The general definition of an isomer is two chemical species that have identical molecular
formulas but are structurally different in some way. With respect to organic chemistry, you have
already learned about constitutional isomers (different connectivity) and conformational isomers
(different rotation about bonds); however, this lab will focus on configurational isomers (a.k.a.
stereoisomers). Stereoisomers are molecules that have the same molecular formula but is
different in how the atoms are arranged in space. Stereochemistry is the study of stereoisomers.
Stereochemistry is a very important topic in organic chemistry and is especially relevant

in the biological sciences. The human body is composed of billions of organic molecules, many
of which contain a specific arrangement of molecules in three dimensional space. If a person
comes into contact with two different stereoisomers, the result may be very different. For
example, if you eat one stereoisomer the taste may be sweet and if you eat the other the taste may
be bitter. This same kind of situation becomes even more important in the pharmaceutical
industry because one specific stereoisomer of a drug will heal you while the other may be very
toxic.
In stereochemistry, there are many terms that are necessary to understand to gain a full
appreciation of the topic. However, a few must be described before attempting to complete this
lab. First of all, a stereogenic carbon2 is a carbon that has 4 different atoms or groups off atoms
attached to it. A molecule that has one stereocenter is said to be chiral (Figure 1). A chiral
molecule is a species that has a non-superimposable3 mirror image (Figure 1). If there is not a
carbon with four different atoms connected, or the mirror images of the molecule can be
superimposed, the molecule is achiral (Figure 2). A molecule that contains two or more
2
The term stereogenic carbon is used interchangeably with asymmetric carbon, stereocenter, stereogenic center,
chiral carbon, chiral center, etc.
3
Superimposable is when two molecules can be overlaid on each other and every part of the molecule matches the
other in all dimentions (3-dimentionally). Therefore, non-superimposable molecules cannot be oriented in any way
to make them match perfectly with the other species.
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Figure 1 A Chiral Molecule
Figure 2 An Achiral Molecule
stereocenters can be chiral or achiral (non-chiral) depending on the orientation of the molecules
in space. A molecule that has two or more stereocenters and is achiral is called a meso
compound (Figure 3). In order to differentiate stereoisomers, a nomenclature has been
Figure 3 Example of a meso Compound
developed based on the Cahn-Ingold-Prelog rules4. The way this is done is by first rotating the
molecule around the stereogenic carbon so that the lowest priority group3 is pointing away from
you. Then you can simply trace around the carbon from highest (1) to lowest priority (3). If the
trace is clockwise, then it is labeled ‘R’ and if counterclockwise, it is labeled ‘S’ (Figure 4).
4
Refer to text book for assigning priority based on Cahn-Ingold-Prelog rules.
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Figure 4 Two Examples of Labeling a Molecule R or S
An alternate way to represent organic molecules three dimensionally was developed by

Emil Fischer during his studies of carbohydrates. This representation is currently referred to as a
Fischer projection (Figure 5). In this representation, all the vertical bonds are treated as dashes
Figure 5 Fisher Projection
(going away from you) and all horizontal bonds are considered as wedges (coming towards you).
It is common practice in this representation that the carbon chain makes up the vertical bonds
and the functional groups are in the horizontal positions.
In today’s lab, model sets will be used to build some simple organic molecules containing
stereogenic carbons. This will aid in the visualization of organic molecules in three dimensions
and help in understanding the assigning carbons as R or S. You will be asked to draw the
perspective structure and/or the Fischer projections for several molecules and assign R or S for
stereogenic centers as well.
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STEREOCHEMISTRY
Worksheet
Part A: Draw the perspective structure and/or Fischer projection for the following molecules:
Compound Perspective Structure Fischer Projection
(R)-2-bromobutane
(S)-2-bromo-2-chlorobutane
(2R,3S)-2-bromo-3-chlorobutane
(2R,3S)-2,3-dibromopentane
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Worksheet (continued)
Compound Perspective Structure Fischer Projection
meso-3,5-dibromoheptane
meso-2,5-dibromo-3,4-dimethylhexane
meso-3,4-dimethylhexane
meso-3,4-dibromo-3,4-dichlorohexane
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Worksheet (continued)
Compound Perspective Structure
(1S,2S)-1,2-dibromocyclohexane
(1R,3S)-1-bromo-3-chlorocyclohexane
(1R,2R)-1-bromo-2-chlorocyclohexane
(1S,3S)-1-bromo-3-methyl-cyclohexane
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Part B: In the boxes provided, indicate whether the carbon with the (*) is R or S. For the two
compounds that have two stereocenters, label in the third box meso or not meso.
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STEREOCHEMISTRY
Pre Lab Questions
1. Label each of the following molecules as chiral (C) achiral (A) and/or meso (M).
2. Use the molecule below to answer the following questions:
a) Draw a circle around the chiral centers in the molecule.
b) How many possible stereoisomers are there for the molecule (hint 2n rule)?
c) Is there the possibility for this molecule to exist as a meso compound?
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INFRARED SPECTROSCOPY
For discussion of infrared spectroscopy (IR), refer to the chapter containing IR in the text book.
Pre Lab Questions
1. Define the following terms:
a. Wavenumber:
b. Absorbance:
c. Percent transmittance:
2. For each of the following functional groups, give the wave number range where a peak would
show up (some may have more than one characteristic peak):
a. Alcohol
b. Carboxylic acid
c. Sp3 C-H
d. Sp2 C-H
e. Aldehyde
f. Alkene
g. Amine
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RECRYSTALLIZATION
Introduction
Recrystallization is a widely used purification technique for powders and crystalline

solids. The technique is ideal for purification after large scale synthesis, where large amounts of
crude product are obtained, and is also used when it is necessary to obtain ultra pure samples for
a variety of analytical techniques.
The recrystallization technique relies on the difference in solubility of the substrate and
the impurities to separate them. It is for this reason that the choice of solvent becomes very
important. Ideally, the best solvent will be one that, at a specific temperature, will dissolve either
the substrate or the impurity, but not both.
There are three common cases that are encountered when attempting to use
recrystallization for purification.
Situation 1: The substrate and the impurities are both soluble in hot solvent
but only the impurities are soluble in the cooled solvent.
In this case, both the substrate and impurities are dissolved in hot solvent first. Subsequently,
the mixture is cooled slowly and the less soluble material will crash out of solution
(recrystallize). If the less soluble material is the desired substrate that means that the impurities
are still dissolved in the cooled solvent. Ultimately, the crystallized solid can be separated from
the impurities by performing a simple filtration to collect the solid.
Situation 2: The substrate and the impurities are both soluble in hot solvent
but only the substrate is soluble in the cooled solvent.
In this case, the technique begins the same as for situation 1 with the difference being that
the less souble material is now the impurity. This means that the desired substrate will be still
dissolved in the cooled solvent. Filtration, in this situation, will be done to remove the impurity
and the substrate can be recovered by evaporating the solvent.
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Situation 3: The impurities are insoluble in the hot solvent.
In this situation, hot solvent is added until all the soluble material is dissolved. Any
insoluble impurities are then removed by performing the filtration while the solvent is still hot.
The substrate is then recovered by evaporating the solvent.
The situations described above are somewhat ideal cases. In reality, it is rare to
encounter such a simple system. More often the substrate and the impurities are both very
soluble in hot solvent, and slightly soluble in cold solvent. In this case, the crude material
(substrate and impurities) are dissolved in the hot solvent of choice and the mixture is cooled
very slowly. A filtration step is then carried out to collect the crystallized solid. The filtrate at
this point will contain the desired substrate and some fraction of impurities. Although the sample
at this point may not be 100 % pure, it will contain fewer impurities than the original sample.
The process can then be repeated as many times as needed to obtain a sample with the desired
purity level.
In today’s experiment, a contaminated sample of acetanilide will be purified using the
recrystallization technique. A sample of acetanilide, containing sugar and sand as impurities, will
be purified. The sample will therefore contain two soluble and one insoluble species in hot
solvent. Water will be used as the purification solvent. In water, at room temperature, sand is
insoluble, sugar is highly soluble and acetanilide is slightly soluble. After performing the
recrystallization, the percent recovery of acetanilide will be determined. In addition, melting
point will be used to determine the purity of the acetanilide recovered from the crystallization.
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RECRYSTALLIZATION
1. Obtain the sample of impure acetanilide and add 1.2 g of the sample to a 25.0-mL Erlenmeyer flask
(label the flask ‘A’).
2. To the same flask, add a magnetic stir bar and approximately 15 mL of deionized water.
3. While stirring, begin heating the solution on a hot plate.
4. In the meantime, in a separate beaker, add 5-10 mL of deionized water and place the beaker
on the hot plate.
5. a. If it appears that all soluble materials have dissolved in the boiling solvent (only the sand
remains undissolved), move on to step 6.
b. If the soluble material has not dissolved in the boiling solvent, use a pipette to add hot
water (from the beaker on the hot plate) drop-wise to the Erlynmeyer flask until all the
soluble material dissolves (only the sand remains).
6. Set up a vacuum filtration with a small Büchner funnel and 125 mL filter flask, wet the filter
paper with a small amount of water.
a. Vacuum filtration is usually used to isolate desired material but in today’s lab it is being
used to remove the sand and filter the hot liquid very quickly.
7. After the filtration, immediately place the filter flask back on the hot plate and heat again
until the solid dissolved.
8. Turn off the heat and allow the flask to cool very slowly to room temperature (15 to 20
minutes).
9. After the flask reaches room temperature, place it in an ice bath (a bigger beaker with ice and
a little water) for about 5-10 minutes.
10. Collect the crystals on a weighed piece of filter paper using vacuum filtration (Buchner
funnel). Leave the collected solid in the filtration setup for about 10 minutes or until dryness
is reached.
11. Measure the mass of the collected sample and take the melting point to determine its purity.
12. If the melting point range is larger than 5 degrees, perform a second recrystallization on the
collected crystals.
13. Calculate the percent recovery of acetanilide (based on total mass of impure sample).
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RECRYSTALLIZATION
Data Sheet
Name________________________________ Date________________
Partner(s) Name(s):
General Observations:
Mass of the starting sample: _______________
Mass of purified crystals: _______________
Melting point of the purified crystals: _______________
Percent recovery of acetanilide from the sample: _______________
Post Lab Questions
1. Assuming that you recovered 100% of the acetanilide in the sample, how much of the mass
of the original sample was made up of impurities?
2. Based on the melting point obtained for your purified sample, what can you conclude about
the purity of the sample?
3. Why was it necessary to filter very quickly to remove the sand?
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RECRYSTALLIZATION
Pre Lab Questions
1. Complete the following table:
Compound Structure Solubility in Hot Water Solubility in Cold Water
Acetanilide
Sugar
2. What is the literature (known) melting point for acetanilide?
3. A student performed a recrystallization to purify a crude sample from a reaction. The amount
of crude material collected from the reaction was 13.56 grams. After the purification, the student
collected 8.97 grams of extremely pure material.
a. What is the percent recovery of the desired material?
b. Is it possible to determine how much of the desired material

remained in solution after the filtration?
4. The solubility of acetanilide in hot water is 5.5 g / 100 mL at 100oC and its solubility in cold
water is 0.53 g / 100 mL at 0oC. What would be the maximum theoretical percent recovery
from the crystallization of 2.5 g of acetanilide from 50 mL of water? Show the calculation.
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NUCLEOPHILIC SUBSTITUTION REACTIONS
Introduction
Nucleophilic substitution is a class of reactions that gets much attention in sophomore
organic chemistry and most text books (if not all) contain at least one chapter dedicated to the
topic. Simply stated, a substitution reaction is where one part of a molecule is replaced by
another group (Scheme 1). This class of reaction is introduced in
Scheme 1 Substitution Reaction
basic chemistry classes and usually involves inorganic salts where A is a cation and B and C are
counter anions. The organic counterpart to this reaction is the nucleophilic substitution reaction
(Scheme 2) and involves one neutral component (the electrophile)
Scheme 2 Nucleophilic Substitution Reaction
and a second component that can either be neutral or negatively charged (the nucleophile).
There are three main criteria that must be met for this reaction to take place; 1) X must be
bonded to an sp3 carbon, 2) the X in R-X must be a good leaving group (i.e. Cl, Br, I, etc.), and
3) Y must have a pair of electrons that can be used to make the new R-Y bond (i.e. a negatively
charged atom or a neutral heteroatom with a lone pair of electrons). There are several other
factors, however, which determine the efficiency of the reaction. Issues such as steric hindrance
on either the nucleophile or the electrophile and how willing the nucleophile is to share its
electrons (nucleophilicity) will dictate how well the reaction will proceed.
In addition to affecting the feasibility of the reaction, the electrophile also determines the
reaction mechanism. Recall from lecture that there are two possible mechanisms by which
substitution reactions can occur (SN1, or SN2, Scheme 3). In the SN1 process, the leaving group
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leaves first resulting in the formation of a carbocation intermediate. Subsequently, the cation is
attacked by the nucleophile. For this process, not only must the leaving group be very good (i.e.
able to support a negative charge very well) but the carbocation intermediate must be stabilized
by the R group. The SN2 process does not produce an intermediate and happens in a concerted
process whereby
Scheme 3 SN1 and SN2 Mechanisms
the nucleophile is forming the new bond simultaneously with the leaving group bond breaking
(see the transition state). In this process, the steric hindrance that is the important factor. If the
R group and/or the nucleophile are very bulky, the process will slow down significantly or
possibly not happen. In summary the relative rates for the two types of mechanisms are:
SN2 process: CH3 > 1 > 2 >>> 3
SN1 process: 3 > 2 > 1 >>> CH3
As can be seen, the relative rates of these follow opposite trends. It is typically
understood that a methyl halide will not undergo a reaction under SN1 conditions and 3 alkyl
halides will not undergo a reaction under SN2 conditions. In addition, the nucleophilic
substitution reaction will never take place on an sp2 carbon under standard conditions (either SN1
or SN2 conditions).
The predictability of the reaction mechanism at the extremes (3, 1, or methyl) is very
straightforward for either SN1 or SN2. However there is the matter of the 2 alkyl halides to think
about. In this case it is usually the leaving group or reaction conditions (i.e. solvent) that dictate
which mechanism the reaction will follow.
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In today’s lab, several alkyl halides will be investigated experimenatally to determine
whether they prefer the SN1 or SN2 reaction process. In order to do this, one must be able to alter
the conditions to favor either the SN1 or SN2 process.
The SN2 conditions will be to treat an alkylhalide with sodium iodide in acetone (Scheme
4). Under these conditions, the iodide ion is the nucleophile. Sodium iodide is
Scheme 4 SN2 Conditions
soluble in acetone whereas the byproduct NaX, where X = chlorine or bromine, is not soluble in
acetone. Therefore, if the the substitution takes place, a precipitate will be observed.
The SN1 conditions involve the use of a solution of silver nitrate (AgNO3) in ethanol
(Scheme 5). Under these conditions, the silver will coordinate with the halogen
Scheme 5 SN1 Conditions
to aid in its “leaving” and the ethanol will act as a weak nucleophile. Remember that in order for
the ethanol to attack, the halide must leave first (see Figure 3, SN1). Silver nitrate is soluble in
ethanol whereas the silver halide salt (AgX) is not. So, if the reagent is able to undergo the SN1
reaction (forming a stable carbocation intermediate), then the precipitate of AgX will be
observed. However, if no precipitate is observed, then step 2 cannot take place.
Using the conditions described above, you can now evaluate several alkyl halides,
qualitatively, to determine their capacity for undergoing the substitution under either SN1 or SN2
reaction or both. In addition, if no precipitate is observed initially while the solution is at room
temperature, the reaction will be heated slightly to see if the increased energy will allow the
reaction to proceed. Depending on the substrate, the reaction rate under the experimental
conditions may vary and doing this experiment will give some insight into the rate at which the
38
reactions occur. (Remember to think about the structure of the alkyl halide and what result you
expect while performing each experiment).
39
SN2 Conditions
1. Using a hot plate, heat a beaker of water to approximately 45 – 50C.
2. Obtain 8 small test tubes and label them according to the alkyl halide that will be
tested.
3. To each of the test tubes, add 1 mL of the solution of 18% sodium iodide in acetone.
4. Add 5-8 drops of the alkyl halide to each test tube.

a. Shake immediately and determine if a precipitate persists (record results in the data
sheet).
b. After 5 minutes (shaking periodically), (if more and more precipitate forms over
time, indicate in the data table that the reaction is slow). If after 5 minutes no
precipitate is observed, move on to step 5.
i. If precipitate has formed, then consider the study of that alkyl halide complete.
5. For the alkyl halide(s) with no precipitate, place the test tube in the previously heated
beaker of water and heat for an additional 5 minutes (shaking periodically).
6. Record the results in the data table and remember to indicate if the reaction seemed to
be slow or fast after heating.
SN1 Conditions
1. Clean the 8 test tubes (or use a different set of 8) and label with the alkyl halide that
will be tested (same as step 1 for the SN2 conditions).
2. To each of the test tubes, add 1 mL of the 1% silver nitrate in ethanol solution.
3. Add about 5-8 drops of the alkyl halide to each test tube.
a. Shake immediately and determine if a precipitate persists (record results in the data
sheet).
b. After 5 minutes (shaking periodically), (if more and more precipitate forms over
time, indicate in the data table that the reaction is slow). If after 5 minutes no
precipitate is observed, move on to step 4.
i. If precipitate has formed, then consider the study of that alkyl halide complete.
40
4. For the alkyl halide(s) with no precipitate, place the test tube in the previously heated
beaker of water and heat for an additional 5 minutes (shaking periodically).
5. Record the results in the data table and remember to indicate if the reaction seemed to
be slow or fast after heating.
41
SN2 DATA TABLE
Substrate 1 2 3 4 5 6 7 8
1-bromo-2- 2-chloro-2-
Name 1-chlorobutane 1-bromobutane 2-bromobutane 3-bromopropene 1-bromopropene Bromobenzene
methylpropane methylpropane
RT*
50C*
*If the precipitate does not persist immediately, record the approximate amount of time at the given temperature it took for the
precipitate to form.
42
SN1 DATA TABLE
Substrate 1 2 3 4 5 6 7 8
1-bromo-2- 2-chloro-2-
Name 1-chlorobutane 1-bromobutane 2-bromobutane 3-bromopropene 1-bromopropene Bromobenzene
methylpropane methylpropane
RT*
50C*
*If the precipitate does not persist immediately, record the approximate amount of time at the given temperature it took for the
precipitate to form.
43
Post Lab questions
1. Compare the reactivity of substrates 1 and 2 (Br vs Cl as leaving group) for both SN1 and SN2
conditions.
2. Compare the reactivity of substrates 2, 3, and 4 (1 vs 2 vs 3) for both SN1 and SN2
conditions.
3. Compare the reactivity of substrates 4 and 5 (Br vs Cl as leaving group) for both SN1 and SN2
conditions.
4. Compare the reactivity of substrates 2 and 6 (1 vs allylic) for both SN1 and SN2 conditions.
5. Comment on the reactivity of substrates 7 and 8 for both SN1 and SN2 conditions.
44
Pre Lab Questions
1. Fill in the table below. In the expected results, indicate if you think the reaction will
require heat (i.e. the reaction will go, but will happen at a slower rate).
Expected Results
Substrate Structure 1, 2, 3, or sp2
(SN1, SN2, both, or neither)
1. 1-chlorobutane
2. 1-bromobutane
3. 2-bromobutane
4. 1-bromo-2-
methylpropane
5. 2-chloro-2-
methylpropane
6. 3-bromopropene
7. 1-bromopropene
8. bromobenzene
45
Montgomery College – Takoma Park/Silver Spring Campus
Proton NMR
For discussion of nuclear magnetic resonance spectroscopy (NMR), read the chapter containing
NMR in the text book.
Pre Lab Questions
1. Define the following terms:
a. Chemical shift
b. Integration
c. spin-spin splitting
d. N+1 rule
e. Shielded and Deshielded
46
SIMPLE & FRACTIONAL DISTILLATION

Introduction
Distillation is a separation technique often used for purification of substances based on
differences in their boiling points. Distillation has many practical uses and is widely used in the
petroleum industry (crude oil refined to fuels) as well as in the spirits industry (used in the
process of making vodka, bourbon, gin, rum, etc.) Briefly, distillation is carried out by heating a
crude mixture to boiling, condensing the vapor, and collecting the cooled vapor (distillate) in a
separate container. A common setup for distillation is represented in Figure 1.
Figure 1 Common Distillation Setup
A simple distillation works well when there is a large difference between the boiling
points of the two compounds trying to separate. If the difference in the boiling point of the two
components to be separated is small, the separation becomes more difficult. One method to
alleviate this problem is to perform many successive distillations until the desired purity is
achieved. This can be very tedious and time consuming. Another way to accomplish this task is
to change the distillation apparatus slightly. In most simple distillations, the distance the vapors
have to travel through the distillation column to reach the condenser is very short. In addition,
there is very little surface area for the vapors to condense on along the way. One can achieve
47
better separation by either increasing the length of the distillation column and/or the surface area
within the column along the way. Increasing column length involves simply joining multiple
columns together of using a column of longer initial length. To increase the surface area in the
distillation column, one can use a fabricated column containing several glass inserts connected to
the inside of the column or by physically inserting a copper or steel sponge in the column.
Figure 2 shows the modified distillation columns.
Figure 2 Distillation Setup with Longer Column and with Sponge
The term used to describe the effect of the sponge or elongating the column is theoretical
plates. The number of theoretical plates is determined by the total number of surfaces between
the crude material and the condenser where the liquid and gas phase are in equilibrium (i.e.
giving the material more places to interact with or condense on before it reaches the condenser).
The presence of the sponge in the column increases the number of theoretical plates and allows
for better separation of the components.
Theory
How does distillation work to separate compounds? To understand, let’s consider an ideal
solution of two volatile components (A and B). In an ideal solution, the components are assumed
to be miscible without interacting with one another. Such solutions follow Raoult’s law which
states:
PA  NA  PA
Where PA is the partial vapor pressure of A in solution, NA is the mole fraction5, and PA, is the
5
The mole fraction of a mixture component is the number of moles of the component of interest divided by the total
number of moles in the liquid mixture. For example NA = moles A / (moles A + moles B)
48
vapor pressure of pure A. The same is true for component B. Therefore, following Dalton’s law
of partial pressures the total vapor pressure is:
Ptot  PA  PB
Recall now the ideal gas law which states:
PV  nRT
This can be used for both components of the mixture as well as the mixture as a whole. For
example, PT V  nT RT and PAV  nA RT . Here nt is the total number of moles in the mixture
(nT = nA+nB). So if we are interested in the ratio PA to PT we can rearrange and combine the two
ideal gas law equations to get first:
nT RT n RT
PT  ; PA  A
V V
and then:
n A RT n A RT
PA V V
 
PT nT RT na  nb RT
V V
Because R, T, and V are constant values in the system we can simplify the equation substantially
to:
PA nA

PT n A  n B 
You may recognize the right-hand side of the above equation from the footnote on the previous
page as the mole fraction of a or NA from Raoult’s law. Therefore we can simplify even further
to:
PA
 NA
PT
This can then be used to determine the partial pressure of A in a mixture by simple
rearrangement of the equation to:
PA  N A PT
49
Additionally, it can be used to determine the mole fraction of a component in a mixture by
rearrangement to6:
PA
NA 
PT
To demonstrate the practical use of these equations consider the following. Assume that at a
given temperature, the vapor pressure of pure A is 800 mmHg and that of pure B is 1200 mmHg,
and we are starting with a 50/50 liquid mixture of A and B. Then, the total vapor pressure is
equal to:
Ptot  PA  PB  NA  PA  NB  PB
Ptot = 0.50 x 800 + 0.50 x 1200

Ptot = 400 + 600 = 1000 mmHg
Now we can determine the mole fraction of A (NA) in the vapor mixture:
NA = 400 / 1000 = 0.40
The vapor is 40 % A and 60 % B. The vapor has indeed a different composition (40/60) than the
starting mixture (50/50.)
6
The equation at this point is referring to the mole fraction in the gas phase.
50
Experiment
Today’s experiment will utilize a different setup than previously described (see Figure 3)
but will work in a similar way.
Figure 3 Distillation Setup for Today’s Experiment
In this experiment, you will be given a sample containing a 1:1 ratio of ethyl acetate and
propyl acetate. A simple distillation (no sponge) and a fractional distillation (with sponge) will
be performed and the distillate analyzed by GC to determine which method results in a better
separation of the mixture components.
51
You will work as groups of 4. Two of you will do the simple distillation, and two will do the
fractional distillation.
1. Prepare the setups for simple and fractional distillations as shown in Figure 3 above.
2. Have the instructor check your setup. If setup is correct, the instructor will give you the
acetate mixture.
3. Add a magnetic stir bar and ~5 mL of the acetate mixture to the 10 mL round bottom flask.
a. Do not throw away or lose the stir bar at the end of the lab.
4. Using a hot plate and an aluminum block, begin heating the sample (150C setting on the hot
plate).
a. Use a thermometer to monitor the temperature of the aluminum block.
b. Increase heat slowly as needed until the distillate reaches the Hickman still.
c. Try to maintain a temperature where the distillate drops are observed at a rate of about 5
drops per minute.
5. Record the temperature (thermometer on the distillation setup) when drops start to condense
in the Hickman still.
6. When 10 to 15 drops are collected, transfer the distillate to a vial (put on the cap to avoid
evaporation) using a pipette and turn off the heat.
7. Run a GC of the starting mixture to find the retention times of the two components and
record them on the data sheet.
8. Run a GC of the collected sample from each of the simple and fractional distillations.
9. Record the retention times and areas for each peak and calculate the percent of the
components in each sample.
52
Data Sheet
Name________________________________ Date________________
Partner(s) Name(s)_____________________________________________________
Injection of Starting Mixture
Compound Retention Time (min)
Component 1
Component 2
Injection of Sample from Simple Distillation
Retention time
Peak Area Percentage
(min)
Injection of Sample from Fractional Distillation
Retention time
Peak Area Percentage
(min)
Post Lab Questions

1. Based on the results from the data collected, which distillation setup is better for separation of
the two liquids?
53
Pre Lab Question
1. Consider a situation where you have a mixture of compound A (bp 80.0oC) and B (110.0oC)
and assume the mixture is an ideal solution (i.e. Raoult’s law applies: PA = PoA XA). At 80oC, the
vapor pressures for the two liquids are PoA = 850 mmHg and PoB = 350 mmHg.
(a) Calculate the total vapor pressure of a 1:1 mixture of compound A and compound B.
(b) What is the percent composition of the two compounds in the vapor phase.
2. Which distillation method would be predicted to be a better purification technique (simple

distillation or fractional distillation)? Give an explanation.
54
Montgomery College Takoma Park/Silver Spring Campus
DEHYDRATION OF CYCLOHEXANOL
Introduction
There are several ways to prepare alkenes (organic compounds containing a carbon-
carbon double bond) in organic chemistry. When studying reactions of alkyl halides, you
learned to prepare an alkene using the elimination reaction (Scheme 1). You
Scheme 1 Elimination Reaction of Alkyl Halides
should remember that this reaction proceeds via an E1 or E2 type mechanism process depending
on the nature of the base and/or alkyl halide involved. Another type of reaction that results in an
alkene is the dehydration of an alcohol (Scheme 2). The
Scheme 2 Dehydration of an Alcohol
dehydration of an alcohol requires the use of a strong acid such as H2SO4 or H3PO4 to catalyze
the reaction. The alcohol will be protonated by the acid thus making it asubstrate with a good
leaving group (H2O). All dehydration reactions begin the same way, by protonation of the
alcohol oxygen, but the subsequent step in the reaction will proceed via an E1 or E2 type
mechanism depending on the class of alcohol being used. If the alcohol is 2 or 3, the reaction
follows an E1 (two step) mechanism whereas 1 alcohols proceed via an E2 (concerted)
mechanism. To demonstrate this, consider the dehydration of 2-methylpropan-2-ol (3) and 1-
butanol (1) using sulfuric acid (Scheme 3 and 4). After protonation of the 3 alcohol, a stable 3
carbocation is formed by losing an equivalent of H2O. Subsequently, the conjugate base of
sulfuric acid will deprotonate the β-hyrdogen to form the alkene.
55
Scheme 3 Dehydration of a 3 Alcohol
Scheme 4 Dehydration of a 1 Alcohol
As stated above, the initial step of the reaction for any dehydration is protonation of the
alcohol. For the 1 alcohol (Scheme 4), this is no different, however this class of alcohol cannot
lose an equivalent of water because the resulting 1 carbocation is too unstable. It is for this
reason that the mechanism follows the concerted E2 type process where the base pulls off the β-
hydrogen, the alkene is formed and the H2O leaves all in one step.
The reaction that will be performed in today’s experiment will be the dehydration of
cyclohexanol using phosphoric acid as the catalyst (Scheme 5). As noted in Scheme 5, the
boiling point of the product is significantly lower than the boiling point of the starting alcohol. It
is for this reason that the reaction will be performed using a simple distillation setup (see
experimental below) whereby the product will be collected as the reaction progresses. While
56
Scheme 5 Dehydration of Cyclohexanol
heating the reaction, as the product begins to form, it will begin to travel (in the vapor phase) out
of the reaction flask and into the distillation column. By using this technique to perform the
reaction, the product will be purified directly and the cyclohexene obtained should be very pure.
57
1. Add 6.4 mL of cyclohexanol ( = 0.962 g/mL), 1.2 mL 85% H3PO4, and a magnetic
stir bar (spin vane) to a 10 mL round bottom flask.
2. Attach the round bottom flask to the bottom of a simple distillation setup as shown
below.
3. Insert a thermometer so that the bottom of the thermometer is level with the bottom
opening of the Hickman still.
4. Using a hot plate and aluminum block, begin stirring and heat the round bottom flask
to 200 C (use a thermometer to measure the temperature of the aluminum block).
5. After the product condenses in the Hickman still, remove the cap of the side arm and
using a glass pipette, transfer the product to a previously weighed vial (record weight
on the data sheet).
a) Keep the vial containing the product in an ice bath and be sure to cap the vial
to avoid evaporation.
6. Replace the cap on the side arm and continue to collect the product in the Hickman
still.
58
7. Repeat step 5 and 6 until only about ~2 mL of liquid remains in the round bottom
flask.
8. Remove the distillation setup from the heat and allow it to cool to room temperature.
9. After the apparatus is cooled, remove the round bottom flask and add 10% Na2CO3
dropwise until no more CO2 bubbles are observed.
a) This step is to neutralize the acid. Na2CO3 (sodium carbonate) is a weak
organic base and the gas produced is CO2
10. Discard the neutralized solution in the waste container and clean the round bottom
flask and distillation setup for use in step 14.
11. Remove the vial containing the distillate from the ice bath and transfer the contents of
the vial to a 25 mL Erlenmeyer flask.
12. Add 2-3 mL of saturated NaCl to the flask and swirl gently for 30 seconds.
13. Allow the two layers to separate and remove the bottom aqueous layer using a
pipette.
14. Repeat steps 12-13 one time and transfer the crude material remaining in the
Erlynmeyer flask to the 10 mL round bottom flask.
15. Attach the round bottom flask to the distillation setup and perform a second
distillation to purify the cyclohexene.
a. This time maintain the temperature of the aluminum block at ≤100C.
16. As the liquid distills, transfer the purified product (from the Hickman still) to a vial
with known mass (vial with cap).
a. Collect the material until the round bottom flask is almost empty.
17. Measure the mass of the vial containing the cyclohexene (with the cap), record the
value on the data sheet and calculate the percent yield.
18. Take an IR spectrum of the product.
59
Bromine Test
19. To the remaining product in the vial, add a few drops of 1.0 M Br2 in methylene
chloride.
a) If the alkene is present, the bromine will immediately react and the brown color
will disappear. (Record results on the data sheet)
20. Discard the contents of the vial in the waste container.
60
Data Sheet
Name________________________________ Date________________
Partner(s) Name(s)_____________________________________________________
Mass of empty vial with cap__________________
Mass of vial (with cap) containing product__________________
Mass of cyclohexene obtained__________________
Percent yield__________________
Bromine test (circle one): brown color remained brown color disappeared
61
Post Lab Questions
1. Analyze the IR spectrum and point out the significant peaks that correspond to the cyclohexene
structure (i.e. sp2 C-H’s, sp3 C-H’s, C-C’s, C=C, etc).
2. How could IR be used to determine the product obtained was contaminated with
starting material?
3. What purification technique could be used if the product of the reaction was not free of
impurities?
62
Pre Lab Questions
1. Fill in the appropriate data in the table below and calculate the theoretical yield. (Use
the amounts of materials that will be used from the experimental section above)
Molecular Weight
Theoretical yield
amount
mols
density/concentration
(if applicable)
Equivalents (mol ratio)
2. Explain how IR can be used to determine if the product collected was cyclohexene.
63
HYDROBORATION
Introduction
As you have learned in lecture, an alkene is a very versatile functional group that can be
used to prepare a diverse array of other functional groups. The hydroboration of an alkene
(Scheme 1) is effectively the addition of H and OH across a carbon-carbon
Scheme 1 The Hydroboration Reaction
double bond. The reaction produces an alcohol where the regiochemistry favors the anti
Markovnikov product (i.e. the resulting OH ends up on the least substituted carbon).
The simplest reagent capable of accomplishing the hydroboration is borane (BH3). The
BH3 is generally available commercially as a Lewis acid/Lewis base complex with an ether (e.g.
tetrahydrofuran (THF) as shown in scheme 1). It is important to note that BH3 is capable of
performing the reaction with three equivalents of an alkene (see Scheme 2 below) but only one
B-H is necessary for each reaction to take place. Since only one B-H is necessary to do the
reaction, often times two of the H’s are replaced with bulkier alkyl substituents. By increasing
the size of the substituents on the boron, the regiochemistry can be improved significantly.
As mentioned above, one BH3 can react with three alkenes based on the fact that there are
three B-H bonds. For discussion of the mechanism of the hydroboration (Scheme 2 and 3),
consider the alkene but-1-ene.
The reaction begins by simultaneously forming a bond from hydrogen to one carbon and
carbon boron bond to the other carbon (Scheme 2). The three hydrogens are colored blue, red
and green to emphasize the three different hydroboration processes. The final product from the
hydroboration step of the reaction (before workup with peroxide) is tributyl borane. It should be
noted here that after one hydroboration step, one butyl group is added to the boron and thus
becomes more sterically hindered. So, as reaction progresses, the regioselectivity of the reaction
improves drastically.
64
Scheme 2 Mechanism of the Hydroboration
the
The workup of the reaction involves the addition of hydrogen peroxide under basic
conditions. This is the part of the reaction where the boron is ultimately replaced by an OH
resulting in the final alcohol. The mechanism is shown in Scheme 3.
Scheme 3 Mechanism of the Workup with Peroxide
Under basic conditions, one oxygen of the hydrogen peroxide is deprotonated and will attack the
boron resulting in a negatively charged boron species. Subsequently, there is rearrangement in
65
which an alkyl group migrates to the boron-bonded oxygen and an equivalent of hydroxide ion is
produced. This step is repeated two more times giving tributylborate. Under aqueous basic
aqueous conditions the three alcohols are then freed from the boron to yield the desired alcohol
(3 equivalents) and boric acid.
In today’s experiment, the hydroboration of hex-1-ene will be performed (Scheme 4)
using a borane-THF complex. The theory states that the regiochemistry will be
Scheme 4 Hydroboration of Hex-1-ene
anti Marknovikov and, thus, the major product predicted is hexan-1-ol. The possible side
product of this reaction is hexan-2-ol. IR of the isolated material will be taken and compared to
literature spectra to determine if only the predicted major product is formed.
66
HYDROBORATION
1. Equip a 5-mL conical vial with a magnetic stir bar (spin vane) and add 250 µL of
hex-1-ene.
2. Close the vial with a septum and cap and begin stirring.
3. Using a 1.0 mL syringe fitted with a 18 gauge needle, add 1.0 mL of 1.0 M BH3.THF
DROPWISE over a period of one minute.
a. Discard the syringe and the needle in the red sharps disposal container.
4. Stir the reaction mixture for 10 minutes.
5. To the reaction mixture, add about 10-15 drops of acetone (while stirring) and stir for
3 minutes.
a. The acetone will react with any excess BH3 to stop the reaction.
6. After 3 minutes, add 3 drops of water and then, using a micropipette, add 250 µL of
3 M NaOH.
7. Using a micropipette add 250 µL of 30% H2O2 DROPWISE over a period of one
minute and stir with no heat for 2 minutes.
8. After 2 minutes, heat the mixture on a hot plate (using an aluminum block) to 60C for
5 minutes.
a. Place the conical vial in the open cylinder in the aluminum block and monitor the
temperature of the block by placing a thermometer in the open small whole on the block
(start time when the temperature reaches 60C).
9. After 5 minutes, add 1 mL of saturated NaCl solution and continue heating for two
minutes.
a. The NaCl solution will extract any aqueous material in the mixture away from the
organic products.
10. Remove the reaction mixture from the heat and cool it to room temperature.
11. Once at room temperature, add 1.0 mL of diethyl ether and stir for one minute using a
cooled hot plate/stirrer.
67
12. After about 1 minute, stop stirring and allow the two layers to separate (ether layer
on top and aqueous layer on the bottom) and remove the aqueous layer using a glass
pipette.
13. Repeat the extraction two more times by adding 0.5 mL of saturated NaCl, stir for
one minute, allow the layers to separate, and remove the aqueous layer.
14. After the final extraction and removal of the aqueous layer, pass the remaining
organic layer (ether layer) through a drying column and collect the filtrate in a
(previously weighed) 50 mL beaker.
a. A drying column is prepared using a glass pipette by first plugging it with a small
piece of cotton, adding 0.2 cm of sand followed by ~3 cm (3-4 fingers high)
anhydrous sodium sulfate.
15. Rinse the reaction vial with ~0.5 mL of ether and pass this through the same drying
column and collect the filtrate in the same small beaker.
16. Place the beaker containing the combined dried organic layer on a warm (65C hot plate
setting) hotplate in the hood to evaporate the ether.
17. Measure the final mass of the small beaker containing the final product and obtain an
IR spectrum of the product.
68
HYDROBORATION
Data Sheet
Name________________________________ Date________________
Partner(s) Name(s):
Mass of empty beaker__________________
Mass of beaker containing product__________________
Mass of product obtained__________________
Percent yield__________________
Calculations
69
Post Lab Questions
1. Compare the experimental IR with the printed IR’s for hexan-1-ol and hexan-2-ol.
a. What conclusion can be drawn about the purity of the experimental product? (i.e. is
it one product or a mixture of products?)
b. What peaks in the IR were important to determine the purity of the product (list a
few peaks and indicate the part of the molecule the peaks correspond too)?
c. Comment about the regioselectivity of the reaction.
70
HYDROBORATION
Pre Lab Questions
1. Fill in the appropriate data in the table below and calculate the theoretical yield. (Use
the amounts of materials that will be used from the experimental section above)
Molecular Weight
Theoretical yield
amount
mols
density/concentration
d=0.673 g/mL cnc = 1.0 M
(if applicable)
Equivalents*
* remember that one equiv. of BH3 can react with three

equiv. of the alkene.
2. Look up and print the IR spectra for hexan-1-ol and hexan-2-ol. These will be used for
comparison to the experimental product. (hint: you can use the SDBS online data base)
71
Montgomery College Takoma Park/Silver Spring Campus
EXTRACTION: MACROSCALE SEPARATION
Introduction
Extraction is a commonly used method to separate two compounds from each other by
taking advantage of their varying solubility in two different solvents. The extraction is usually
performed at the completion of a reaction either immediately before or during the purification
step. The most common extraction technique is a liquid-liquid extraction where two immiscible
solvents are used to separate desired products from impurities. In an ideal extraction involving
two compounds, compound (X) would only be soluble in solvent 1 while the other compound
(Y) would only be soluble in solvent 2. However, there are many situations that arise where
compound X is slightly soluble in solvent 2 and compound Y is slightly soluble in solvent 1.
When this situation arises, more than one extraction step is necessary to completely remove the
compound from the solvent in which it is slightly soluble.
The above mentioned case where a compound is slightly soluble in both solvents can be
represented mathematically by looking at the solubility in both solvents, how many grams of
each compound there is and the amount of each solvent used. The ratio of the amount of the
compound in each solvent is represented as a partition coefficient (K).
[ X ] solvent1
K
[ X ] solvent2
m X (in1)
Vsolvent1
Therefore: K 
m X (in2)
Vsolvent2
m X (in1) Vsolvent2
Rewritten: K  *
m X (in2) Vsolvent1
As an example, consider a situation where K=1.5. If 6.0 grams of X is dissolved in equal

amounts of solvent 1 and solvent 2 (compound X is more soluble in solvent 1; K>1) then there
will be 3.6 grams of X in solvent 1 and 2.4 grams of solvent 2. After separating the two solvents,
another extraction can be done. If another equal volume of solvent 1 is added to solvent 2
72
(which still contains 2.4 grams X) then X will partition its self between the two solvents again
and this will result in solvent 1 containing 1.44 g X and solvent 2 will contain 0.96 g. This result
is because the partition coefficient (K) remains the same. More X can be extracted by solvent 1
if the volume is increased during any extraction but executing multiple extractions with smaller
volumes of solvent proves to be more efficient. [If the same extraction is done using a 2:1 ratio
of solvent 1 to solvent 2 (compared to two equal volume extractions), the amount of material
remaining in solvent 2 is 1.5 grams which is larger than 0.96 grams from above and therefore not
as efficient]. At the end of the extraction step the solvent is usually removed by evaporation and
the solid placed under vacuum to remove any residual solvent. Therefore it is more economical
and environmentally friendly to use smaller volumes of solvent. The ultimate goal of an
extraction is to ensure full recovery of the desired material so using enough solvent is necessary
to an extent. However at some point, the amount of material recovered by performing more
extractions becomes negligible and repeating them is no longer productive.
In a typical organic synthesis, the reactions are performed in organic solvents and upon
completion of the experiment, the “work up” involves the addition of reagents dissolved in
aqueous solutions. This inherently introduces water soluble materials to the organic products.
At this point, the chemist can either extract the aqueous materials from the organic solvent or
extract the organic material out of the aqueous solution. Remember, the ultimate goal is to
obtain a pure organic product at the end of the reaction. Often times there are multiple organic
products formed from the reaction (i.e. major and minor products). When this occurs, other
purification techniques such as chromatography or recrystallization may be required.
As the title of this experiment indicates, the extraction that will be performed in this lab is
a macroscale extraction. The scale of the extraction will be larger than for any reaction you will
perform in future labs. However, it is more typical of the scale of reactions performed in a
research laboratory. You will be required to perform an acid base reaction followed by an
extraction to separate a 50/50 mixture of benzoic acid and benzil (Figure 1). Both of the
Figure 1 Benzoic Acid and Benzil
73
compounds in figure 1 are are soluble in organic solvents. The solvent used for today’s lab will
be diethyl ether. If enough diethyl ether is added to the mixture of these compounds, both will
completely dissolve. Due to their similar solubilities, a chemical modification is necessary to
make the separation possible. Only benzoic acid has a functional group that is easily and
reversibly modified. This derivatization will be done by performing an acid base reaction. Upon
treatment of the mixture with an aqueous solution of sodium hydroxide, the carboxylic acid
proton will be deprotonated resulting in the sodium carboxylate salt which is highly soluble in
aqueous solvent (Figure 2). At this point, the two compounds can be separated by simply
Figure 2 Reaction and Separation
separating the two solvents. After separation, the aqueous layer can be made acidic by adding
aqueous acid to the solution resulting in the neutral benzoic acid being reproduced. The product
will then crash out of the aqueous solution because benzoic acid is insoluble in water. At this
point, the benzoic acid can be collected by filtration whereas the benzyl, which has remained in
the ether phase throughout, may be isolated by evaporating the solvent.
After performing the reaction and the extraction, the percent recovery of each compound
74
can be calculated based on the total amount of the mixture you began with. In addition, with the
knowledge of the composition of the starting mixture, you will be able to determine the success
of the extraction. Melting point will also be used to determine the purity of the recovered
material.
75
EXTRACTION: MACROSCALE SEPARATION
A. Acid-Base Reaction and Extraction
1. Add approximately 1.0 g of the 50:50 mixture of benzoic acid/benzil (record exact amount
used) to a 25 mL Erlenmeyer flask and add enough diethyl ether to dissolve the mixture.
2. Obtain a separatory funnel, stopcock, and glass stopper. Apply grease to the stopcock and
stopper (taking care not to clog the hole in the stopcock) and assemble the setup as shown in
figure 3.
Figure 3 Extraction Setup
3. With the stopcock closed, transfer the ether solution from the 25 mL Erlenmeyer flask to the
separatory funnel. Rinse the Erlenmeyer flask with small amount of ether to insure
quantitative (complete) transfer to the separatory funnel.
4. Add 5 mL of 5% NaOH to the separatory funnel, insert the stopper, and mix the contents by
gently inverting the funnel several times.
a. After each inversion, carefully vent the funnel by opening the stopcock while inverted (be
careful to point the open end of the funnel away from yourself and others around you).
5. When the solution no longer makes a hissing sound when venting, place the funnel in
the ring stand and allow the layers to separate.
6. Open the stopcock slowly and collect the aqueous (bottom) layer in a 25 mL Erlenmeyer
flask. (be careful when performing this step to not allow any of the ether (top) layer to leave the
separatory funnel).
7. Repeat steps 4 – 6 combining all the aqueous layers in the same flask. Label the flask and set
aside for the isolation of benzoic acid step below (part B).
8. To remove any remaining undesired aqueous soluble material, add 5 mL of saturated NaCl
solution to the ether layer (still in the separatory funnel).
76
9. Mix the contents gently as described in step 4 above, venting often.
10. After thorough mixing, place the separatory funnel in the ring stand allowing the layers to
separate.
11. Collect the aqueous (bottom) layer in a small beaker and set aside to be discarded in the
waste container.
12. Into a separate 25 mL Erlenmeyer flask, collect the remaining the ether layer for the isolation
of benzil step below (part C).
B. Isolation of Benzoic Acid
1. To the flask containing the combined NaOH aqueous layer extractions, add 6 M HCl (5 – 10
mL) until the solution becomes strongly acidic.
a. Test the pH of the solution using litmus paper. The paper will turn red if the solution is
acidic.
2. After the solution is very acidic, place the flask in an ice bath for 15 minutes.
3. Collect the crystals by vacuum filtration using a Büchner funnel.
4. While under vacuum, wash the crystals with 5 mL of ice cold water and let the crystals remain
under vacuum for 15 minutes or until they become very dry.
6. Measure the mass of the collected crystals and calculate the percent recovery based on the
mass of the original mixture.
7. Measure the melting point to determine the purity of the recovered benzoic acid.
C. Isolation of Benzil
1. To the flask containing the ether layer, add enough anhydrous MgSO4 to absorb any
remaining water in the solution.
a. Add small amounts of MgSO4 at a time. Swirl the flask after each addition and keep
adding more until the MgSO4 continues to float freely around in the solution after swirling
has stopped.
2. Using gravity filtration, remove the MgSO4 and collect the ether in a small beaker with a
predetermined mass (25 or 50 mL).
3. Wash the filter paper containing the MgSO4 with 2 – 3 mL of ether to rinse any remaining
benzil into the beaker.
77
4. Add 1 or 2 boiling chips to the beaker containing the ether solution and heat the beaker gently
(70-80oC) on a hot plate under the hood.
5. Once the ether has evaporated, allow the beaker to cool to room temperature.
6. Measure the mass of the beaker containing the crystals and calculate the mass of the collected
crystals and calculate the percent recovery based on the mass of the original mixture.
7. Measure the melting point to determine the purity of the recovered benzil.
78
EXTRACTION: MACROSCALE PROCEDURE
Data Sheet
Name________________________________ Date________________
Partner(s) Name(s):
Initial mass of benzoic acid/benzil mixture: ________________
Initial mass of the benzoic acid: ________________
Initial mass of the benzil: ________________
Benzoic Acid Benzil

Mass Recovered (g)
Melting Point (oC)
Percent Recovery (%)
Overall Percent Recovery (%)
Post Lab Questions
1. Based on the percent recovery of benzoic acid and benzil, what do they indicate about the ratio
of the two in the original sample?
2. How closely does the ratio based on percent recovery match the known 50:50 mixture?
3. Comment on the reliability of this method to determine the percent composition of a sample.
(for example, what is the error and where might this error ocuured?)
79
EXTRACTION: MACROSCALE PROCEDURE
Pre Lab Questions
1. A student in the lab was excited to have finally isolated 20.0 grams of the desired product X
from the reaction. During all the excitement, the student accidentally dropped the beautiful
yellow crystalline product into a beaker containing 50.0 mL of deionized water. In order to
recover the product, the student decided to perform an extraction with ether. Compound X is
soluble in both ether and water where the partition coefficient of X between ether and water is
4.0.
a. The first extraction was done using 50.0 mL of ether. After this extraction, how much
of compound X will remain in water?
b. A second extraction was performed using 25.0 mL of ether. After this extraction, how
much of compound X will remain in the water?
c. If no more extractions were performed at this point, how many grams of compound X
would have been extracted into ether?
d. What is the percent recovery of compound X?
80

CH 203 Lab Manual SS - 2012

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CH 203 Organic Chemistry I

MELTING POINT DETERMINATION

If a broad MP range is observed (≥3C), it could be due one or more of the

Part I: Melting Point Determination of benzoic acid.

2. Insert one capillary tube in the melting point apparatus.

Part II: Determination of the Identity of an Unknown Sample.

1. Obtain an unknown sample and record the sample number.

3. Record the MP range for the unknown on the data sheet.

5. Identify the unknown.

Compound MP (C) Compound MP (C)

benzoic acid 122-124 urea 132-135

acetanilide 113-115 salicylic acid 158-161

succinimide 123-125 triphenylmethanol 163-165

Melting Point Range of Benzoic Acid

Melting Point Range of Unknown

Selected Compounds with Closest Melting Points

Mixed Melting Points

CH 203 Organic Chemistry I

THIN LAYER CHROMATOGRAPHY (TLC)

Distance traveled from the origin (cm) Rf

TLC Plate Data

1. Complete the following table:

Compound Acetaminophen Acetyl salicylic acid Mandelic acid

a) Which compound is more polar if the stationary phase is silica gel?

CH 203 Organic Chemistry I

Stereochemistry is a very important topic in organic chemistry and is especially relevant

Figure 2 An Achiral Molecule

An alternate way to represent organic molecules three dimensionally was developed by

Compound Perspective Structure Fischer Projection

Compound Perspective Structure Fischer Projection

Compound Perspective Structure

Pre Lab Questions

2. Use the molecule below to answer the following questions:

a) Draw a circle around the chiral centers in the molecule.

c) Is there the possibility for this molecule to exist as a meso compound?

CH 203 Organic Chemistry I

Pre Lab Questions

1. Define the following terms:

CH 203 Organic Chemistry I

Recrystallization is a widely used purification technique for powders and crystalline

3. While stirring, begin heating the solution on a hot plate.

Mass of the starting sample: _______________

Mass of purified crystals: _______________

Melting point of the purified crystals: _______________

Percent recovery of acetanilide from the sample: _______________

Post Lab Questions

3. Why was it necessary to filter very quickly to remove the sand?

1. Complete the following table:

Compound Structure Solubility in Hot Water Solubility in Cold Water

2. What is the literature (known) melting point for acetanilide?

a. What is the percent recovery of the desired material?

b. Is it possible to determine how much of the desired material

CH 203 Organic Chemistry I

NUCLEOPHILIC SUBSTITUTION REACTIONS

Scheme 1 Substitution Reaction

4. Add 5-8 drops of the alkyl halide to each test tube.

CH 203 Organic Chemistry I

Pre Lab Questions

1. Define the following terms:

e. Shielded and Deshielded

CH 203 Organic Chemistry I

SIMPLE & FRACTIONAL DISTILLATION