Experiment 5

Effects of solvents on Nucleophiles (I-) and (Cl-)

Introduction
In the following experiment a substitution reaction was performed using 1-Bromobutane LiI and LiCl
as reactants where LiI and LiCl are substituting me and Cl for Br to make 1-Iodobutane and 1chlorobutane as products. This experiment will be done using three different solvents (acetone, EtOH,
and water) to test the solvents effects on which product is more favored. Based on information from
masterorganicchemistry.com the solvent is effecting the Nucleophile (in this case I- and Cl-). A polar
protic solvent is one that can participate in hydrogen bonding with the Nucleophile, if possible,
stabilizing the Nucleophile. In the case of halides F is stabilized the by hydrogen bonding and thus is the
least nucleophilic when in a polar protic solvent where as I is the strongest of the halides. Polar aprotic
solvents do not participate in hydrogen bonding so nucleophilicity is determined by basicity. In the case
of Halides F is the most unstable and thus is the most nucleophilic in an aprotic solvent where as I is
the weakest. Continuing the experiment the product was filtered and all solvent was removed from the
organic product so that a clean sample could be tested in a gas chromatograph. Gas chromatography is
a way to measure the quantity of individual components in a solution by separating them based on
different solubility, polarities and boiling points and the application for gas chromatography range
from pharmaceuticals to fuels. According to a video on AgilentChem, a YouTube channel, gas
chromatographers works with five essential parts of the machine. The first is a chosen non-reactive
carrier gas which carries the test sample through the machine. The second is a heated injection port
where the sample is added and heated as it enters, this temperature slowly rises until no more
components are being recorded. The third is the Column which is a tube containing a viscus liquid on
the sides of the tube that separates the sample by virtue of solubility and is the heart of the machine.

The forth is the detector which detects the amount of separated sample entering it of the duration it
entered. The fifth is a computer and monitor that uses a program to interpret and display the results.

The results of gas chromatography are based on boiling point and polarity as mentioned before, yet
since boiling point is based off of polarity the dominant property that separates most substances is
boiling point. Given this the prediction of the order of products for the GC results is based off of the
table below the first would be 1-chlorobutane, then 1-Bromobutane, ending with 1-Iodobutane.

Alkyl Halides
1-chlorobutane
1-Iodobutane
1-Bromobutane

Alkyl Halides Information of Products

molar masses
Boiling Point (at 760 mm Hg)
92.5673 g/mol
78.5 deg C
184.01873 g/mol
130 deg C
137.01826 g/mol
101.3 deg C

Procedure
Each group was assigned different solvents (acetate, EtOH, or Water), for this procedure acetone was
used.
A reflux station was set up for this experiment using a 25ml round bottom flask, and the following where
added to the flask: 1ml of 1-Bromobutane, 1ml of LiI and LiCl, 1ml of solvent acetone, and boiling chips.
The mixture was given 90 minutes of reflux time. Once 90 minutes passed the flask, with the reflux
condenser connected, was immersed into a water bath. Mixture was set aside.

2ml of pentane and 1ml of mixture where added to a screw cap vial. Next 1ml of distilled water was
added and vial was shaken. After letting the vial sit two layers appear, organic and aqueous, the lower
aqueous halve was removed using a pipette. This proses of adding distilled water was repeated 3 times.
The organic layer was then dried using 1ml of brine (saturated sodium chloride solution) and then further
dried with a small amount of anhydrous magnesium sulfate. The solution was filtered through a pipette
stuffed with a small amount of glass wool and collected in another screw cap vial. The vial was then sent
to a gas chromatographer to determine its makeup.

Data
Graph for GC results

Pentane
1-Bromobutane
1-Iodobutane
1-chlorobutane

Alkyl Halide
1-chlorobutane
1-Bromobutane
1-Iodobutane

Retention Time (min.)

1.80
2.23
2.95

Peak Area
8.78E+01
8.06E+02
3.66E+02

Proportion
6.97%
63.98%
29.05%

Proportions vs Retention Time

70

63.98

60

Proportions

50
40
29.05
30
20
6.97

10
0
0

0.5

1.5

2.5

3.5

Retention Time

Ration of Iodide:Chloride

1-Bromobutain

9.05

Iodide:Chloride
4
5

10

Discussion
The results show that LiI (Iodide) was the better nucleophile by a factor of 9.05:1. Given that the
resulting molecules are identical in shape the only way to know why LiI is a better nucleophile is to
look at what makes a better nucleophile. There are four key elements to nucleophilicity Charge,
Electronegativity, Solvent, and Steric hindrance. In this case both nucleophiles have a charge. In the
case of electronegativity the lower the better thus, iodine is better than chlorine. This is because a
nucleophile is gaged at how good it can donate a pair of electrons and the higher its

electronegativity the less willing it is to part with those electrons making it less effective as a
nucleophile. The solvent if polar protic will hinder a nucleophile based on how electronegative it is
the stronger it is the more it will participate in hydrogen bonding with the solvent lowering its
nucleophilicity, if the solvent is polar aprotic than it does not participate in hydrogen bonding and
will not hinder electronegative nucleophiles but no longer stabilizes them making them more
reactive. In this case acetone is polar aprotic, thus it does not hinder chlorine, the more
electronegative molecule, any more than it does iodine but since it is not stabilized it is now slightly
more reactive. And in this case both nucleophiles are bonding to the same electrophile so steric
hindrance is the same. To conclude this entire reactions preference was affected by the
electronegativity of the atoms and by the polar aprotic solvent and based on the information
present the difference in electronegativity had a greater impact on preference than the solvent
used, thus LiI is the better nucleophile.

Citations
Information on solvents and nucleophiles
JAMES. "What Makes A Good Nucleophile?" Master Organic Chemistry RSS. N.p., n.d. Web. 29 Nov.
2015.
Information on Gas chromatography
Provided by video on AgilentChem YouTube channel
Channel URL: https://www.youtube.com/channel/UCxuPDTVp1YUQPO_pny41KRA
Video URL: https://www.youtube.com/watch?v=piGSGkcwFAw&feature=youtu.be
Image provided by: http://teaching.shu.ac.uk/hwb/chemistry/tutorials/chrom/gaschrm.htm
Information on nucleophiles
James. "What Makes A Good Nucleophile?" Master Organic Chemistry RSS. N.p., n.d. Web. 01 Dec.
2015.