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Preparation and Purification of an Alkyl Halide

Joshua L. Chuaa*
Department of Chemical Engineering, University of the Philippines Diliman, Quezon City, Philippines

ABSTRACT
Tert-butyl alcohol was reacted with a hydrogen halide (hydrochloric acid) to produce tert-butyl chloride. The reaction was carried out
via nucleophilic substition (specifically, an SN1 mechanism). Cold concentrated HCl was added in excess to tert-butyl alcohol.
Afterwards, solid NaHCO3 and anhydrous CaCl2 were added to purify the compound and to maintain the product as an alkyl halide.
Finally, the crude tert-butyl chloride was distilled to obtain pure tert-butyl chloride. 2.93 g of tert-butyl chloride was obtained after
distillation. With a theoretical yield of 9.812 g, the % yield was 29.86%. While crude tert-butyl chloride was successfully synthesized
from tert-butyl alcohol, the experimenters failed to obtain a significant amount of pure product, with a percent yield of <30%.

*Corresponding author. Mobile: 09166406270

E-mail address: joshua.chua.923@gmail.com

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1. Introduction
Alcohols are an organic compound wherein a hydroxyl
group (-OH) is bonded to a sp3 hybridized carbon. When
reacted with hydrogen halides (such as HCl), alcohols can
undergo a nucleophilic substitution reaction to form an
alkyl halide.
In this experiment, tert-butyl alcohol is reacted with
concentrated hydrochloric acid to form tert-butyl
chloride. This reaction occurs via an S N1 mechanism. SN1
reactions are nucleophilic reactions where the ratedetermining step is unimolecular (McMurry, 2015).
Alkyl halides are simply alkanes containing one or
more halogens. While normal alkanes are non-polar, alkyl
halides are polar compounds. This is due to the
electronegative nature of halogens. In the C-X bond, the
carbon exhibits a partial positive charge while the
halogen exhibits a partial negative charge.
Alkyl halides can be classified into 3 types: primary,
secondary, and tertiary. Primary alkyl halides are
compounds wherein the carbon that is bonded to the
halogen is bonded to only 1 other carbon. Likewise, the
carbon with the halogen attached in secondary alkyl
halides are bonded to 2 other carbons while in tertiary
alkyl halides the carbon is attached to 3 other carbons.
An example of a tertiary alkyl halide is tert-butyl chloride,
the final product of this experiment.
As far as physical properties go, alkyl halides have
higher boiling points compared to alkanes. This is due to
the increase in size of the molecule by replacing a
hydrogen with a halogen. Alkyl halides are also soluble
in organic solvents but are only slightly soluble in water.
In the experiment, tert-butyl alcohol is reacted with
concentrated hydrochloric acid to synthesize tert-butyl
chloride. Afterwards, tert-butyl chloride is purified via
distillation.

A 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. A thermometer bulb
was placed just below the side arm of the distillation
head.
A round bottom flask was chosen to place the sample
in. A water bath was used to regulate the temperature. 23 pieces of boiling chips were added to the flask.
The water supply was turned on and the sample in the
flask was slowly heated to a gentle boil. The boiling point
was recorded. The heat was adjusted so that the
distillation occurred at a rate of 2 drops of distillate per
second.
The first few milliliters of distillate were discarded
while the fraction that distilled at the desired
temperature was collected. This was recorded as the
boiling point of the volatile component. The distillation
set-up was maintained until right before the sample was
dried up. The heat source was removed when the sample
started to boil. Finally, the set-up was allowed to cool
before dismantlement.
3. Results and Discussion
In the experiment, a tertiary alcohol (tert-butyl
alcohol) was reacted with a hydrogen halide
(concentrated hydrogen chloride) to synthesize an alkyl
halide (tert-butyl chloride). This reaction was done via an
SN1 mechanism. The mechanism is shown in the figure
below:

2. Materials and Methods

2.1. Generation of Crude tert-Butyl Chloride
10 mL of tert-butyl alcohol and 20 mL of cold
concentrated HCl were placed in a dry 50 mL separatory
funnel. The mixture was swirled gently while occasionally
relieving the internal pressure by opening the stopcock.
The mixture was allowed to stand undisturbed for 20
minutes. The separation of layers was facilitated by
adding 3-5 mL of 6 M NaCl solution. The aqueous layer
was then discarded. 1-2 drops of water was added to the
separated layers to determine the identity of the organic
layer.
The collected filtrate was dried with a small amount of
anhydrous CaCl2. Small amounts were added until it
clumped together.
The crude tert-butyl chloride was decanted into a dry
25 mL round bottom flask. A few boiling chips were
added and the flask was distilled.
The fraction that boiled at 49-52C was collected in a
pre-weighed vial and cooled in an ice bath. The percent
yield was determined and the solubility of the purified
product was tested with water. The wastes were then
disposed into the appropriate waste containers.
2.2. Preparing a Simple Distillation Apparatus

(Source: http://academic.keystone.edu/JFalcone/tBuClPrepv2_files/image004.gif)

Fig. 1. SN1 reaction mechanism for tert-butyl alcohol

and hydrochloric acid
Aside from tert-butyl chloride, methylpropene may
also be produced as a side product. This may happen if
the reaction is done at elevated temperatures. To avoid
the formation of methylpropene, the concentrated HCl is
cooled down before being added to the tert-butyl alcohol.
Another method of limiting the amount of methylpropene
is to occasionally open the stopcock of the separatory
funnel when swirling. This is done in order to release the
gaseous methylpropene.
Cold concentrated HCl was added in excess for two
reasons. First, as stated above, the cooled down HCl
prevents the production of other unwanted side products.
Second, adding the HCl in excess ensures that the
reaction proceeds in the forward direction (i.e., towards
the formation of tert-butyl chloride).
After collecting the organic layer, solid NaHCO 3 was
added to it. This was done in order to react with and

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neutralize the excess HCl. Aqueous NaHCO 3 wasnt used

for it would reverse the reaction and produce tert-butyl
alcohol.
After the addition of NaHCO 3, anhydrous CaCl2 was
added to the crude product. Adding CaCl 2 prevents the
hydrolysis of the tert-butyl chloride. Otherwise, the
product may revert back to the original alcohol. The
CaCl2 also absorbs any excess water.
To isolate and protect the target compound from
possible impurities, as well as to purify the product, the
sample was distilled using a simple distillation set-up.
Boiling chips were used during distillation to provide
nucleation sites so that the liquid boiled smoothly. A
continuous flow of water was also part of the set-up so
that the sample condenses after heating and not
evaporate.
After distillation, the mass and percent yield of tertbutyl chloride was obtained. Below is a table of the
masses of the beginning and end products, along with
the theoretical and % yield.
Table 1
Masses of Reactants & Products and Yield
Mass of tert-butyl alcohol,7.858 g
g
Mass
of
tert-butyl2.93 g
chloride, g
Theoretical yield
9.812 g
% yield
29.86 %
The relatively low yield can be attributed to the
volatility of alkyl halides, such as tert-butyl chloride
(Pavia, 2005). Leaving the product alone and exposed to
open air may have evaporated some of the alkyl halide.
Performing the experiment faster and minimizing the
exposure time of the product to open air may be done to
increase the percent yield.
Below is a table of the observed and measured
physical properties of tert-butyl alcohol and tert-butyl

chloride.

Table 2
Physical Properties of tert-Butyl Alcohol and tert-Butyl
Chloride
Properties
tert-Butyl Alcohol
tert-Butyl
Chloride
Color
colorless
colorless
Solubility in water
soluble
insoluble
Boiling point
82.41C
51C
It was observed that the tert-butyl chloride is less
soluble in water than the original alcohol and also has a
lower boiling temperature.
4. Conclusion and Recommendations
Crude tert-butyl chloride was successfully
synthesized from tert-butyl alcohol and concentrated
hydrochloric acid. However, in terms of the amount of
tert-butyl chloride produced, the experiment was a
failure because of the low percent yield. The
methodology can be improved by storing the crude tertbutyl chloride when not in use to prevent evaporation of
the product.
References
Pavia, D.
McMurry, J. Organic Chemistry, 7th ed.; Thomson: California,
2008; pp 372-380.
Rapra Technology. Rigid PVC Foams: A New Twist to an Old
Technology. Cellular Polymers III. 1995, 134.
UC Davis ChemWiki. http://chemwiki.ucdavis.edu/ (accessed
March 2, 2016).

Appendices
(See attached data sheet)