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Preparation And Purification Of An Alkyl Halide

Grefaldia, Camille E.a,, Gonzales, Anne Nicole S.a
aCollege of Home Economics, University of the Philippines Diliman, Quezon City, Philippines

ABSTRACT
Alkyl halides are essential in everyday lives and serve many purposes in different institutions such as in homes,
hospitals, schools, etc. They can be synthesize from various methods although preparation from alcohol is the most
generally used. The purpose of the experiment was to synthesize tert-butyl chloride from tert-butyl alcohol by reacting
with concentrated HCl and then purifying using simple distillation. Tert-butyl alcohol and concentrated HCl were placed
and mixed in a separatory funnel where two layers of liquid formed, one was the organic layer where the tert-butyl
chloride was in and the other layer is the aqueous layer. The two layers can be determined using a water drop test. The
layers were then separated. The organic layer was reacted with solid NaHCO3 and then anhydrous CaCl3 was added. The
compound was then purified by simple distillation. The theoretical yield was 9.74g and the yield obtained was 0.11g
giving a percent yield of 1.13%.

1. Introduction
Organic chemistry is the study of structure,
properties, composition, reactions and preparations
of carbon-containing compounds. A lot of carbon-
containing compounds are synthesized because
they are useful in variety of different industries. For
example, in pharmaceutical industry, organic
chemists synthesize new compounds that are
potential drugs use to treat diseases.
Alkyl halides are abundantly found in nature and are
used in variety of everyday products such as aerosol
propellants, refrigerants, anaesthetics and PVCs.
Preparation of alkyl halides from alcohol is an
experiment where the reaction uses an alcohol and
a hydrogen halide as the starting materials for
preparing an alkyl halide. Hence, the objective of this
experiment is to synthesize an alkyl halide from a
tertiary alcohol and hydrogen halide along with the
determination of the yield and purification of the
sample through simple distillation. (Carey &
Guiliano, 2014)
2. Materials and Methods
The materials and apparatus used were: tert-butyl
alcohol, concentrated HCl, solid NaHCO3, icebath,
50-mL separatory funnel, semi-micro distillation
set-up, 50-mL Erlenmeyer flask, thermometer, hot
plate, oil bath, rubber tubing and aluminum foil.
10 mL tert-butyl alcohol and 20 mL cold
concentrated HCl were placed in a dry 50 mL
separatory funnel and swirled gently, then from
time to time relieving pressure by opening the
stopcock (Fig 1, Appendix). The ratio 10:20 was to
make sure that the alcohol reacts completely with
HCl. The mixture were allowed to stand for 20
minutes in order to make sure that the organic
compound and aqueous compound go to their
respective layer. 1 drop of NaCl was added to
facilitate the separation of layers. The aqueous layer
was discarded (Fig 2, Appendix). The organic layer
was determined by performing a water drop test to
any of the separated layer and the layer in which the
water dissolved in was the aqueous layer. The
organic layer was then transferred into a dry flask
that contained a small amount of solid NaHCO3 and
swirled gently then decanted into another dry flask.
The collected filtrate was then dried with the small
amount of anhydrous CaCl2. The crude tert-butyl
chloride was then decanted into a dry 25 mL round
bottom flask and then distilled with the simple
distillation set-up shown in the appendix figure 3.
The simple distillation set-up was prepared making
sure that the water flowed into the bottom of the
condensers cooling jacket and out from the top and
a thermometer bulb placed just below the side arm
of the distillation head. The round-bottom flask of
appropriate volume was used and big enough so the
sample filled or 1/3 of its volume. The flask was

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then placed in an oil bath to regulate the
temperature. The sample was then placed in the
flask along with 2-3 pieces of boiling chips making
sure that the sample liquid was not hot. It was made
sure that the water flows through the condenser and
there were no loose glass joints and that they were
all well-fitted. The sample was gently heated to a
gentle boil until the temperature remained constant
at the boiling point. The boiling temperature was
recorded. The vapors and condensate passed
through the side arm into the condenser, where
most of the vapor condensed into liquid, and
dripped from the adapter into the receiving flask.
The heat was adjusted to that distillation occurred
at a rate of 2 drops distillate per second. The first
few milliliters of distillate were discarded and the
fraction the boiled off at 49-52 degree Celsius were
collected in a pre-weighed vial cooled in an ice bath.
It was made sure that it was not distilled to dryness.
The sample was removed from the heat source when
the sample started to boil. The distillation set-up
was let to cool before disassembling it. The yield was
then determined and the solubility of the purified
product to water was tested. (IC, 2014)
3. Results and Discussion
Alcohols react with hydrogen halides according to
the general equation:
R OH + H X R X + H OH
R represents the alkyl group and X represents a
halogen. (IC, 2014)
A hydrogen containing halide is always acidic
because it can donate a proton. The order of
reactivity of the hydrogen halides correlates their
acidity: HI > HBr > HCl >> HF. HI is used infrequently
and HF is not a useful reagent for the preparation of
alkyl fluorides. Moreover, tertiary alcohols are
observed to be the most reactive and primary
alcohol is the least reactive: R3COH > R2CHOH >
RCH2OH.
Tertiary alcohols readily react with HCl at room
temperature and produces alkyl halides in high yield
within minutes. On the other hand, secondary and
primary alcohol do not readily react with HCl at fast
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enough rates therefore a more reactive HBr is used
and the reaction takes place at a higher temperature
to increase the rate of reaction compare to the
reaction between a tertiary alcohol and HCl.
The reaction between an alcohol and an alkyl halide
is a type of substitution reaction. The functional
group in alcohol which is a hydroxyl group OH is
replaced or substituted by a halogen, usually Cl or Br
from the alkyl halide. However, the type of reaction
does not tell us the mechanism of the reaction or the
step-by-step method that gives rise to the products.
Figure 4. SN1 reaction mechanism of tert-Butyl
alcohol and hydrogen chloride
Tertiary alcohols such as tert-butyl chloride
undergo SN1 reaction as shown in Figure 4. The
mechanism for this reaction is composed mainly of
three main steps or series of equations.
Step 1 involves proton transfer. Like water, alcohols
have the ability to donate a proton from oxygen and
also accept a proton on oxygen. A proton transfer in
water gives oxonium ion/ hydronium ion, H3O+, in
alcohol it gives an alkyloxonium ion, ROH2+. This
step involves two molecules, HCl and (CH3)3COH
that undergo chemical change, thus the proton
transfer is said to be bimolecular. The intermediate
formed is tert-Butyloxonium ion which is not a

reactant nor a product but rather it lies on the
pathway from reactants and products.
Step 2 in Figure 4 shows a reaction in which
formation of a carbocation (an ion containing a
positively charged carbon) occurs. The
alkyloxonium ion dissociates to a molecule of water
and a carbocation. Only one chemical species
undergoes a chemical change, therefore this step is
said to be unimolecular. The intermediate in this
step, tert-Butyl cation is a relatively unstable species
which is too unstable to be isolated. The reason for
its instability is that the carbon in the carbocation
does not follow the octet rule and only has 6
electrons in its valence shell. However, a carbocation
makes the species electrophilic or electron-loving
which makes it vulnerable to a nucleophilic attack,
which occurs in step 3. (Carey & Guiliano, 2014)
Nucleophiles are Lewis bases that react with
electrophiles because they have an unshared pair of
electrons ready to form bonds. The nucleophile
which is Cl-. This step is bimolecular because there
are two species involved in the reaction which is the
carbocation, tert-butyl cation and the nucleophile,
Cl-. (McMurry, 2012)
Step 2 which is the formation of the carbocation
from the oxonium ion is the slowest step of the three
steps and is the point of highest energy in the energy
diagram throughout the whole reaction so it is called
the rate-determining step. The reaction between
tert-Butyl alcohol and hydrogen halide is said to
follow an SN1 which is proposed by Ingold. SN stands
for substitution nucleophilic follows by 1 or 2, 1
means that the reaction is unimolecular because its
slow determining step only involves one species.
(Carey & Guiliano, 2014)
In the experiment, the separatory funnel used was
closed off with a stopcock. It was necessary as well
as important to perform the experiment in a closed
system because tert-butyl chloride is a highly
volatile organic compound and would evaporate in
an open system ultimately resulting in a lower
percent yield and percent purity simultaneously.
The percent yield calculated(Appendix) of tert-butyl
chloride from this experiment is 1.13% which is
extremely low. This could have been a result of
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various errors. One source of error could have been
the formation of side products from side reactions.
For example, one side product that might have
formed is di-tert-butyl ether. This is shown by the
mechanism below.
Figure 5. Di-tert-butyl ether mechanism
Another side product that might have formed is 2-
methylpropene as shown in the mechanism below:
Figure 6. 2-methylpropene mechanism
Again, the presence of these side products would
have competed with the target product and resulted
in a lower yield of tert-butyl chloride. In order to
limit or prevent the formation of these possible side
products, it was made sure that the temperature
remained at a high temperature to make sure that
these side products would not form and only tert-
butyl chloride would be collected. Moreover, the
concentrated HCl used was cold and this was to
prevent the formation of 2-methylpropapane. Also,
HCl being cold was to prevent volatilization of
organic compound and to avoid the sudden release
of heat which is really important because boiling
chips would have avoided this however, boiling
chips were not used. Excess, concentrated HCl was
used in order for the alcohol to completely react
with it and become thoroughly solvated, This would
have been another source of error if HCl was not
cold enough to have prevented these from
occurring. Another reagent used was NaHCO3 which
is commonly used in experiments to neutralize acid
spills. It was made clear that solid NaHCO3 were to
be used instead of an aqueous sodium bicarbonate
as to prevent the addition of water in the sample
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solution by hydrolysis. Furthermore, anhydrous hydrogen bromide, hydrogen iodide,

CaCl2 was used to remove excess water. This was a
necessary step to prevent inaccurate results as the
presence of water would have resulted in a higher
yield than what was actually expected and this
would cause a miscalculation in actual yield and
theoretical yield.
Another method used to prevent inaccuracies was in
the simple distillation set-up itself. It was made sure
that the water flowed continuously all throughout
the distillation part of the experiment. This was
important because it ensured that the condenser
was kept warm throughout and made sure that the
all the vapour condensed into the liquid and
collected in the receiving flask. Otherwise, less
condensation meant less yield of tert-butyl chloride.
(Bruice, 2014)
Some common possible errors were human errors
in reading of the temperature on the thermometer,
contamination of the reagents and the reagents
might not have been up to standards and had low
quality. These could all have resulted in
discrepancies in the results and the reason why the
yield is 0.11g and percent yield, 1.13% is very low
especially if compared to the calculated theoretical
yield, 9.74g.
phosphorus(III) chloride, or phosphorus (IV). Any of
these alternatives might result in a better yield.
References
[1] Carey, Francis A., Giuliano, Robert, M., 2014.
Organic Chemistry 9th Edition. McGraw-Hill, New
York
[2] Bruice. P. 2014. Organic Chemistry 7th Edition.
Pearson, New York
[3] Clark, Jim. 2003(modified in 2015). Replacing
the OH group in Alcohols by a Halogen.
http://www.chemguide.co.uk/organicprops/alcoh
ols/halogen.html. Retrieved on September 21, 2017.
Web.
[4] Institute of Chemistry(IC), 2014 edition. Organic
Chemistry Laboratory Manuel. University of the
Philippines. Diliman
[5] McMurry, John E. 2012. Organic Chemistry,
Chapter 11: Reaction of Alkyl Halides: Nucleophilic
Substitutions and Eliminations. Cengage Learning

4. Conclusion and Recommendations

The objective of the experiment of synthesizing

tert-butyl chloride was met because we were able to
collect a small amount of the target product.
However, the yield obtained in this experiment was
extremely low. Hence, the experiment was deemed
inaccurate in obtaining a higher yield because of all
the possible limitations and sources of error during
this experiment. Therefore, a more careful and
thorough experiment should be done. Moreover,
other alternative methods in purifying alkyl halide
could be performed. For example, instead of using
simple distillation, fractional distillation could be
use which is essentially similar to simple distillation
except that there is a fractioning column (Figure 6,
Appendix) placed between the boiling flask which is
filled with glass or plastic beads improving the
separation of liquids being distilled. Moreover, an
alternative in preparing an alkyl halide was to react
a primary or secondary alcohol to thionyl chloride,
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Appendices

Figure 1. Holding and Venting a Separatory Funnel

Figure 2. Draining the Lower Layer

Figure 3. Simple Distillation Set-up

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Calculations

mass of tert-butyl alcohol(g) = density x volume

= 0.78g/mL x 10 mL
= 7.8g

mmol of tert-butyl alcohol(mmol) = mass /

molar mass
= (7.8g/1000)/74.12mg/mmol
= 105. 23mmol

mass of tert-butyl chloride(g) = weighed vial

after experiment pre-weighed vial
= 33.67g -33.56g
= 0.11g

mmol of tert-butyl chloride(mmol) =

mass/molar mass
= (0.11g/1000)/92.57mg/mmol
= 1.2mmol

theoretical yield(g) = [mol tert-butyl alcohol x (1

mmol tert-butyl Cl/ 1 mol tert-butyl alcohol)] x
molar mass
= 0.10523 mol x (1/1) x 92.57g/mol
= 9.47g

percent yield(%) = (actual yield/ theoretical

yield) x 100%
= (0.11g/9.74g) x 100%
= 1.13%