Experiment 5: Analysis of a Substitution

Reaction by GC
Introduction
Alkyl Halide

Boiling Point (C)

Molar Mass (g/mol)

1-bromobutane

101.30 1

137.02 1

1-chlorobutane

78.500 2

92.556 2

1-iodobutane

130.00 3

184.02 3

Pentane

36.0004

72.146

In this experiment, gas chromatography was used to determine which nucleophiles could
better perform a substitution reaction of 1-bromobutane. Gas chromatography runs liquids
through a very long, coiled tube, and turns them into gases. Usually, the solvent the solution
was in is the first peak. Substances that are smaller with lower boiling points come out of the
tube before other molecules in the solution (Padias 185), creating the second reading. The
larger the molecules become, the longer it takes for them to be read on the machine. Based off
the size and boiling points of the molecules used (noted in the table above), the order will be
pentane, 1-chlorobutane, 1-bromobutane, and finally 1-iodobutane.
Not all nucleophiles are created the same. The trend for nucleophilicity is that it
increases down and to the left of the periodic table ( Wade 266). Therefore 1-iodobutane is a

1-Bromobutane. PubChem. Nov 12 2015. Web Nov 15 2016.

https://pubchem.ncbi.nlm.nih.gov/compound/1-Bromobutane#section=Top.
1-Chlorobutane. PubChem. Nov 14 2015. Web. Nov 15
2016.https://pubchem.ncbi.nlm.nih.gov/compound/8005.
Butyl iodide. Chem Spider. Web. Nov 15 2016.
http://www.chemspider.com/Chemical-Structure.10497.html.
Pentane. Pub Chem. Nov 12 2016. Web. Nov 15
2016.https://pubchem.ncbi.nlm.nih.gov/compound/pentane#section=Top.

better nucleophile than 1-chlorobutane. However, the position of the leaving group has a large
impact on how the reagents react. For substitution reactions of second order (SN2), the less
steric hindrance, the better. The leaving group on the electrophile (the bromide for the
1-bromobutane in this experiment), needs to attached carbon atom with as little substituents as
possible (Wade 271). Because the nucleophile attacks the electrophile from the backside, any
other substituents attacked the the same carbon atom will interfere in the reaction.

Experimental
-Substitution Reaction
A reflux apparatus was set up with a round bottom flask (25 mL). Boiling chips, the
nucleophile (1.0mL), 1-bromobutane (1.0mL), and acetone (1.0mL) were all added to the flask.
The apparatus was set over a steam bath and was allowed to reflux for 90 minutes. It was then
cooled in an ice bath.
-Reaction Workup
Pentane (2.0mL) and the reaction mixture (1.0mL) were both added to the same screw
vial cap. Water (1.0mL) was added to the vial, and then removed via pipette and placed into a
beaker. This repeated a total of three times. A dry organic layer of bring (1.0mL) was added and
removed with a pipette. Then, anhydrous MgSO4 was added to the vial, and was filtered by
putting glass wool into a pipette, and flowing the solution through it into another screw vial cap.
It then was stored for a week.
-Analysis by Gas Chromatography
The reaction was brought to the gas chromatography machine. The machine printed out
the graph of the molecules.

Results

Alkyl Halide

Retention TIme

Peak Area

Proportion (%)

Pentane

3.77

5.97E+00

19.28

1-Chlorobutane

4.45

1.81E+01

58.31

1-Bromobutane

5.47

7.07E+00

22.78

-It can be assumed that 1-iodobutane did not appear on the graph because it did not react well
with the 1-bromobutane. Also, the third peak cannot be 1-iodobutane because if there were any,
1-bromobutane would appear first anyways because it has a lower boiling point and molar mass
than 1-iodobutane.

Only one electrophile was used during the entire experiment, however this hypothetical chart
can show what would have happened. The chloride would decrease as the iodide increased.

Discussion
Within the personal results, the LiCl served as the superior nucleophile, showing a
58.31% proportion on the gas chromatography graph. Even without the graph, it is simple to
predict which nucleophile would extract the bromide easier because it is in a primary position.
The chloride ion is not selective at all, and does not require multiple substances to balance its
charge. The iodide ion, on the other hand, is highly selective, and will attack more substituted
carbon atoms, preferably in the secondary or tertiary position.
Although there were no other nucleophiles were used during this experiment, there are a
few trends that can be predicted. The electrophile does not change the nucleophilicity of either
LiCl or LiI. However. If there were were more electrophiles used, the results would reveal that as
the electrophiles became more substituted, a larger yield of the iodo-alkane would form. The
alkanes with the bromide in the primary position (1-bromobutane and 1-bromo-2-methylbutane)
would form more easily form the chloro-alkanes. The alkane with the secondary bromide
(2-bromopentane) would form almost even numbers of both the chloro-alkane and iodo-alkanes.

The alkane with the tertiary bromide (2-bromo-2-methylbutane) would form much more of the
iodo-alkane than the chloro-alkane.

Lab Notebook