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Angel Navidad 1

Lab No. 4
Effect of solvent polarity on an SN1 reaction
Aim
To determine how the rate of hydrolysis of 2-chloro-2-methylpropane (tert-butyl chlorine,
tBuCl) is affected by the polarity of the solvent used during the reaction.

Hypothesis
If polarity of the solvent is increased, then the rate of hydrolysis of tBuCl will also
increase.

Introduction to theory
tBuCl is a colourless, liquid halogenoalkane at room temperature with structure
http://upload.wikimedia.org/wikipedia/commons/thumb/2/24/Tert-butyl-
chloride-2D-skeletal.png/100px-Tert-butyl-chloride-2D-skeletal.png

The C-Cl bond is polarised, with Cl drawing electrons to itself. When dissolved in a polar
and protic solvent (which can donate protons, H+), like water, the same bond is broken,
yielding a tertiary alcohol and HCl acid:

http://www.organicchem.org/oc2web/lab/exp/sn1/sn1reactions.gif

In the reaction, a negative OH- ion replaces the partially negative Cl atom. This is a
nucleophilic substitution, where the electron-rich nucleophile (OH- anion) attacks the
electron-deficient substrate (the partially positive carbon), replacing another group or
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Effect of solvent polarity on an SN1 reaction
atom (the leaving group):

The reaction of tBuCl with water (hydrolysis) has 3 steps: ionisation of tBuCl to form a
carbocation; bonding of a water molecule to the carbocation (the transition state); and
deprotonation to form the alcohol:
http://3.bp.blogspot.com/-
QcKfkFpbwew/Uoy72UWpC3I/AAAAAAAADRw/gWMuxoim_jo/s1600/Mechanism+for+
hydrolysis+of+tert-butyl+chloride.png

The slower (rate-determining) step only involves one molecule, the substrate, so the
reaction is a unimolecular nucleophilic substitution (SN1). Because of this, the rate of
reaction only depends on the substrate.

The solvent used in substitution reactions, however, determines the nucleophiles
relative strength (the ease at which they donate electrons). This is called the solvent
effect. For SN1 reactions, the solvents ability to stabilise the first transition state (when
the C-Cl bond is partially broken) is proportional to the rate of reaction. By solvating the
partially positive C atom and partially negative Cl atom in the first transition state, the
solvent lowers the energy of that transition state, thus decreasing the first activation
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Effect of solvent polarity on an SN1 reaction
energy. The more polar the solvent used, the more it lowers the first activation energy,
so the faster the hydrolysis of tBuCl proceeds.

Apparatus and materials
1. Stand, burette and burette clamp
2. Magnetic stirrer
3. Stopwatch
4. White card
5. Conical flasks (50 mL, 125 mL, 250 mL)
6. Pipette
7. Funnel
8. Volumetric flask (100 mL)
9. Pasteur pipettes

Chemicals
1. Deionised water
2. Standardised 0.04 M NaOH solution
3. Bromothymol blue indicator solution (in
drop bottle)
4. t-butyl chloride liquid
5. acetone
6. isopropanol

Fig. 1 Titration apparatus

Method and procedure
SAFETY: acetone, isopropanol, tBuCl are inflammable liquids.

Solvent mixtures
1. In separate 100 mL volumetric flasks, prepare the following solvent mixtures by
volume (100 mL per mixture):
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Effect of solvent polarity on an SN1 reaction
50/50 acetone/water 50/50 isopropanol/water
60/40 acetone/water 60/40 isopropanol/water

Carry out separate titrations and data analyses for each solvent mixture.

Titration
1. Obtain a stopwatch, a dropping bottle of bromothymol blue indicator solution, and
a white card (to provide a plain white background when determining endpoints by
titration).
2. In a 250 mL conical flask, place 150 mL of 0.04 M standardised aqueous NaOH
solution. Using this solution and a funnel, fill your burette.
3. With a stopwatch at hand, using a Pasteur pipette, transfer 1 mL tBuCl liquid into
the 100 mL volumetric flask with the solvent mixture. Stopper the flask, shake
well, and start the stopwatch. Transfer the reaction mixture to a 100 mL conical
flask and stopper it. Except when removing aliquots of this reaction mixture, keep
this flask stoppered to prevent evaporation of the volatile liquids.
4. Prepare two infinity time samples by adding a 5 mL sample (Pasteur pipette) of
the reaction mixture to each of two 50 mL conical flasks containing 25 mL of
deionised water. Stopper these flasks securely and let them stand for at least 90
minutes. The high concentration of water in these samples drives the reaction to
completion relatively quickly, so that they can be used to determine the
concentration of HCl, [HCl], present when the reaction is complete (infinite
time). Having two infinity time samples decreases the chances of experimental
error.
5. Remove aliquots of the reaction mixture at the time intervals indicated below. At
each sample time, withdraw a 5 mL sample and place it in a 125 mL conical flask
containing 15 mL of acetone. The hydrolysis reaction is relatively slow in
acetone, so this effectively quenches the reaction. Record the exact time (t) at
which each sample was quenched. Add 3 drops of bromothymol blue indicator
solution to the flask and titrate with the standardised NaOH solution to a blue end
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Effect of solvent polarity on an SN1 reaction
point that persists for 20 seconds. Record the volume of NaOH required to reach
this end point.

50/50 solvent mixtures Collect data every 15 minutes up to 90 minutes, and
then collect a final data point at 115 minutes.
60/40 solvent mixtures Collect data every 20 minutes up to 120 minutes.

6. After completing data collection, titrate the two infinity time samples in the same
way. Record the volume of NaOH solution required to reach the end point.

DISPOSAL: Flush waste solutions down the drain with water.

Data analysis
1. Calculate the concentration of HCl acid at infinity time, [HCl].*
2. Calculate the concentration of HCl acid at each sampling time, [HCl].*
3. Plot (y-axis) vs. time (t) (x-axis). Draw the best straight
line through the points and calculate the slope. From the slope, calculate the rate
constant for the reaction.**
*[HCl] It takes 1 mole of NaOH to neutralise 1 mole of HCl:

So [HCl] = [NaOH].
**k The straight line is given by the linear equation
where is the y-intercept
and is the slope. The rate constant for the reaction would be k.


Variables

Manipulated Solvent mixture
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Effect of solvent polarity on an SN1 reaction
Responding Volume of NaOH solution required to neutralise HCl in the
quenched sample
Controlled Temperature; 0.04 M standardised aqueous NaOH solution; 1
mL tBuCl liquid to 100 mL solvent mixture; sample intervals; 15
mL acetone used to quench.

Predicted results
The rate of all SN1 reactions depend only on 1 concentration, that of the substrate. So
all graphs obtained should resemble those of a first order reaction (a straight line when
ln [substrate] vs. t is plotted).

The slopes (-k) would differ as shown,
with 1 = 50/50 acetone/water (largest
k), 2 = 50/50 isopropanol/water, 3 =
60/40 acetone/water, 4 = 60/40
isopropanol/water (smallest k). This
order reflects their respective
polarities, as per their dielectric
constants (80 for water, 21 for
acetone, 18 for isopropanol). In other
words, solvent polarity would be found
to be proportional to reaction rate (k).

Limitations
1. Fumehood is not available in lab.
2. Temperature control is not possible in lab.

Sources of error
1. Parallax errors while recording volume of NaOH used.
2. Air bubbles in pipette or burette while titrating.
3. Evaporation of volatile liquids while standing in mixture.
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Effect of solvent polarity on an SN1 reaction
4. Mistaking or missing the titration end-point.

Assumptions
1. Assume the dielectric constant is an accurate measure of polarity.
2. Assume no other solvent property (like proton donating capabilities) account for
the solvent effect.