KINETICS OF HYDROLYSIS OF TERT-BUTYL

CHLORIDE


Chemical Concepts
SN1 reactions; solvent effects; chemical kinetics; titration
Green Lessons
Alternative solvent selection recognition of impact of solvent
choice on reaction rate.
Estimated Lab Time: 1.52 hours

Introduction
The solvent in which a reaction is carried out often influences the rate of the
reaction. If the reactant is more stabilized by interaction with solvent molecules than is
the transition state, the activation barrier for the reaction will be increased, and the rate
will decrease. Conversely, if the transition state is more stabilized by solvation than is the
reactant, the activation barrier for the reaction will be decreased, and the rate will
increase. Although solvents can interact with reactants (and transition states) in a
number of ways, two particularly significant interactions are the solvation of ions by polar
solvents and hydrogen bonding between anions and hydrogen bond donating solvents.
In this experiment, you will explore these issues by measuring the kinetics of a
unirnolecular substitution reaction the SN1 reaction between water and tert-butyl
chloride (2-chloro-2-methylpropane) in various solvents. The energy diagram depicting
the course of this hydrolysis reaction, provided on the next page, serves as a convenient
reference for consideration of solvent effects on the rate of this reaction.
Reaction Mechanism
The hydrolysis involves 3 steps:
1. the ionization of the tert -butyl chloride to form a carbocation intermediate;
2. the formation of a high energy transition state between the carbocation and water;
3. the formation of product, tert-butyl alcohol by a hydrogen ion leaving the transition
state complex.
KINETICS OF HYDROLYSIS OF TERT-BUTYL CHLORIDE
2

Hydrolysis of tert-butyl chloride an SN1 reaction

X R
3
C + H
2
O
E
Reaction Coordinate
R
R
R
X

R
3
C
+
+ X
-
+ H
2
O
OH
2
R
3
C + X
-
+
OH R
3
C
+ HX
S
N
1 deprotonation
R
R R
O
H
H
R
R R
O
H
H

Energy diagram for the hydrolysis of tert-butyl chloride
In the first transition state, associated with the slower (rate-determining) step, the
carbon-chlorine bond is partially broken: the chlorine bears a partial negative charge
and the carbon a partial positive charge. The charge-separated nature of the transition
state will be better stabilized by polar solvents than by nonpolar solvents. Thus, ignoring
any differences in solvation of the reactant, increasing the polarity of the solvent
better solvating the polarized transition state and thereby lowering the activation barrier
should increase the rate of this hydrolysis reaction. Similarly, moving to a better
hydrogen bond- donating solvent should allow stabilization of this transition state through
hydrogen bonding with the chlorine, bearing a partial negative charge; again, the rate
C H
3
CH
3
CH
3
Cl
C H
3
C
+
CH
3
CH
3
-Cl
-
C H
3
CH
3
CH
3
O
+
H
H

+ H
2
O
C H
3
CH
3
CH
3
OH
-H
+
tert-butyl chloride
carbocation transtion state
tert-butyl alcohol
KINETICS OF HYDROLYSIS OF TERT-BUTYL CHLORIDE
3
of the hydrolysis reaction should he enhanced. For a summary of SN1 and SN2 reactions,
see Table 1 on page 6.
A common strategy in reducing or eliminating hazards in a synthesis involves
replacing a hazardous solvent with a more benign one. In making such substitutions, it is
important to know that changing the solvent can lead to dramatic changes in reactivity
switching to a greener solvent may either hinder or enhance the desired reactivity.
Similar issues arise when contemplating selection of an alternative reactant or reagent.
This experiment is designed to emphasize these points.


Experimental Procedure

Pre-Lab Preparation

Carry out pre-lab preparations as called for by your instructor.


SAFETY PRECAUTIONS: Acetone, 2-propanol. and tert-butyl chloride are flammable
liquids. Avoid open flames.

In this experiment you will be studying the kinetics of hydrolysis of tert-butyl
chloride in one of four different solvent mixtures: 50/50 acetone/water, 60/40
acetone/water, 50/50 2-propanol/water, and 60/40 2-propanol/water. Your instructor will
assign a solvent mixture for you. By sharing your results with those of your classmates using
other solvent mixtures and considering the classs collective data set, you will be able to
analyze the effect of solvent composition on the rate of this reaction.

Note: The accuracy of your results depends on the experimental care you take. Pay
particular attention to accurate weighing of materials, measuring volumes, monitoring
reaction times, performing titrations, and keeping track of units in your calculations.
Remember, your classmates are relying on you to work carefully and accurately.

Reaction

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 Erlenmeyer flask, place 150 mL of 0.04 N standardized aqueous NaOH
solution. Using this solution and a liquid funnel, fill your burette.


3. Weigh 1 g ( 0.0l g) of tert-butyl chloride into a 100-mL volumetric flask, then dilute to
the line with your solvent mixture assigned by your instructor. Stopper the flask, shake well,
and start your stopwatch. Transfer the reaction mixture to a stoppered Erlenmeyer flask.
Except when removing aliquots of this reaction mixture, keep this flask stoppered to
prevent evaporation.
KINETICS OF HYDROLYSIS OF TERT-BUTYL CHLORIDE
4

4. Prepare two infinity time samples by adding a 5-mL sample (micropipette) of your
reaction mixture to each of two 50-mL Erlenmeyer flasks containing 10 mL of water.
Stopper these flasks securely and let them stand at least one hour while you complete
the next steps. The high concentration of water in these samples drives the reaction to
completion relatively rapidly, so that they can be used to determine the concentration
of HCl present when the reaction is complete (infinite time), which will be represented
as [HCl]

. By working with two samples, you decrease the possibility of being confused by
experimental error.

5. Remove aliquots of the reaction mixture at the time intervals indicated below for your
solvent. At each sample time, withdraw a 5-mL sample and place it in a 125-mL
Erlenmeyer flask containing 15 mL of acetone. The hydrolysis reaction is quite slow in
acetone, so this effectively quenches the reaction. Record the exact time (t) that you
quench each sample. Add 3 drops of bromothymol blue indicator solution to the flask
and titrate with the standardized NaOH solution to a blue end point that persists for 20
seconds. Record the volume of NaOH required to reach this end point.

Data for the 50/50 solvent mixtures should he collected every 15 minutes up to 90
minutes, and then a final data point should he collected at 115 minutes. For the 60/40
mixtures, collect data every 20 minutes up to 120 minutes.

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

Data analysis

1. From your titrations of the infinity time samples, calculate [HCl]

.

2. From your titrations of the aliquots of the reaction mixture, calculate the concentration
of HCI present at each of the sampling times (t), which will be represented as [HCl]t.

3. Plot ln ([HCl]

- [HCl]t) vs. time (t). (Refer to the mathematical background notes

following this experiment if the reasons for constructing this plot are not clear to you.)
Draw the best straight line through the points and calculate the slope. From the slope,
calculate the rate constant for the reaction. Report your rate constant and solvent
composition to your instructor, and obtain rate data obtained by your classmates, both
for your own and for the other solvent mixtures.











KINETICS OF HYDROLYSIS OF TERT-BUTYL CHLORIDE
5
Post-Lab Questions and Exercises

1. Provide the plot of your data as described above and a table summarizing your
kinetic data.

2. Compare the rate constant that you obtained to that reported by other students in
your section by preparing a table comparing rate constants and solvent mixtures.

3. How does your determined rate constant compare with that by your classmates for
the same solvent compositions?

4. How do the rate constants found at different solvent compositions compare?

5. Is the solvent dependence consistent with the proposed mechanism for the SN1
reaction?


Modified July 2, 2012 by Sharmaine S. Cady, East Stroudsburg University



























KINETICS OF HYDROLYSIS OF TERT-BUTYL CHLORIDE
6
Table 1. Summary of Nucleophilic Substitution Reactions

Source: http://128.8.90.214/classroom/chem243/chem243Dr.Mazz/



KINETICS OF HYDROLYSIS OF TERT-BUTYL CHLORIDE
7
Mathematical Data Analysis


The SN1 reaction may be written as follows, where k represents the rate constant
for the forward reaction:

Cl R OH R + HCl H
2
O +
k


At t = 0, [RCl] = [RCl]0 and [HCl]0 = 0, since no RCl has reacted.

At t > 0, [RCl]t = [RCl]0 [HCl]t. For every mole RCl reacted, a mole of HCl forms.
Hence the amount of RCl that remains at time t is equal to the starting amount
minus the amount of HCl formed at time t.

At time = , all of the RCl has reacted to form HCl, so that [RCl]0 = [HCl]

. It is
easier and more accurate to measure [HCl]

than [RCl]0. Hence, Equation 1 can

be written:

[RCl]t = [HCl]

- [HCl]t 1


The rate of formation of ROH is equal to the rate of loss of RCl. Equation 2,
therefore, applies:

2

These rates are dependent on the concentrations of ROH and RCl. This is
inconvenient because the concentrations change as the reaction progresses.
This leads to a nonlinear rate versus t correlation. To compare the rates of
reaction, a constant is needed that is independent of concentration, namely the
rate constant k as shown in Equation 3

3

Rearranging the equation gives the following:

4


KINETICS OF HYDROLYSIS OF TERT-BUTYL CHLORIDE
8

Integrating Equation 4 on both sides from 0 to t, yields

5
Substituting Equation 1 into Equation 5 and using [HCl]

= [RCl]0 results in Equation

6:

6

Rearranging Equation 6 gives Equation 7, which is a straight-line equation of the
form y = mx + b, where m is the slope and b is the y-intercept.

ln ([HCl]

- [HCl]t) ln [HCl]

= - kt

ln ([HCl]

- [HCl]t) = - kt + ln [HCl]

7

If ln ([HCl]

- [HCl]t) is plotted on the y-axis and t is plotted on the x-axis, a

straight line with slope k and y-intercept ln [HCl]

is obtained.