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Lab 5 - Chemical Kinetics

This document describes an experiment to determine the rate constant of an SN1 reaction involving the solvolysis of tert-butyl chloride. Samples will be taken from the reaction at various time points and titrated with sodium hydroxide to determine the amount of hydrochloric acid produced. The data will be plotted as log10(titerinf - titert) versus time to obtain the rate constant from the slope of the linear trendline. Quenching the samples in acetone is necessary to stop the reaction before titration. An "infinity" titer will also be determined by accelerating the reaction to ensure complete conversion.

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Franck Momo
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109 views3 pages

Lab 5 - Chemical Kinetics

This document describes an experiment to determine the rate constant of an SN1 reaction involving the solvolysis of tert-butyl chloride. Samples will be taken from the reaction at various time points and titrated with sodium hydroxide to determine the amount of hydrochloric acid produced. The data will be plotted as log10(titerinf - titert) versus time to obtain the rate constant from the slope of the linear trendline. Quenching the samples in acetone is necessary to stop the reaction before titration. An "infinity" titer will also be determined by accelerating the reaction to ensure complete conversion.

Uploaded by

Franck Momo
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Chemical Kinetics

Rate Equation for the Solvolysis of tert-Butyl Chloride


The rate determining step of an SN1 reaction is the formation of a carbocation
(first order). In the solvolysis of tert-butyl chloride, we may represent the rate of reaction
as the change in alkyl halide concentration divided by the change in time.
Mathematically, the rate equation is as follows:
-d[RX]/dt = k[RX]
Integrating the rate equation gives:
ln[RX]0/[RX]t = kt
where [RX]0 is the concentration of the alkyl halide at the start of the reaction and [RX]t
is the concentration at time t. After some manipulation, the equation becomes:
log10[RX]t = -kt/2.303 + log10[RX]0
Notice that this equation is that of a straight line (y = mx + b).

We will be measuring the appearance of HCl in this experiment, not the


disappearance of RCl. Therefore, for our purposes:
RCl + H2O  ROH + HCl
[HCl]t = [RCl]0 –[RCl]t or [RCl]t = [RCl]0 – [HCl]t
At very large times (t  ∞), [HCl]inf = [RCl]0, since there is no RCl remaining. After
substitution, our equation now becomes:
log10([HCl]inf – [HCl]t) = (-k/2.303)t + log10[HCl]inf
Since the concentration of the acid [HCl] is proportional to the amount (milliliters) of
base (titer) added, we can substitute amount of base (titer) for the concentration of the
acid [HCl].
log10(titerinf – titert) = (-k/2.303)t + log10(titerinf)

Measurement of the SN1 Reaction Rate of tert-Butyl Chloride


A successful kinetics experiment requires both an understanding of the operations
to be performed and advance preparation of many solutions and reagents, as well as
collection of essential apparatus. Kinetics experiments once started must be completed
without interruption. To avoid mistakes, a table should be prepared in which the
laboratory data can be recorded as the experiment progresses.
In the following experiment, the SN1 reaction of tert-butyl chloride with a 50:50
mixture of water and 2-propanol will be examined. In this solvolysis of the chloride, it is
convenient to follow the reaction progress by titrating small samples of the reaction
mixture to determine the amount of hydrochloric acid that has been generated. Because it
takes some time to perform a titration, it is necessary to stop (quench) the reaction before
the sample is titrated. SN1 reaction rates are very sensitive to the amount of water present
in the solvent, going slower the lower the concentration of water, as indicated below:
Solvent half-life
H2O 24 sec
50% H2O - 50% iPrOH 50 min
20% H2O - 80% EtOH 21 hrs
A convenient technique for quenching the tert-butyl chloride solvolysis is to add
the aliquot to an equal volume of acetone, which halves the water concentration and
drastically lowers the rate of solvolysis.
The time at which each sample is quenched must be recorded, so that the times
from the start of the reaction can be calculated and used to determine the rate constant. It
is desirable to titrate several samples from each of the first two half-lives. There is no
point in measuring time intervals with greater precision than is obtained with the
titrations. In this experiment, the half-life is about 50 minutes, so that recording the times
to the nearest half-minute is adequate.
We will need to know the product concentration at “infinite” time. Since the
starting material diminishes by 50% for each half-life, the infinity value can be
approximated with adequate precision by titration of a sample after 8-10 half-lives, which
corresponds to about 99.9% reaction. Another strategy for obtaining the infinity value is
to withdraw a sample and accelerate the rate of the reaction, either by raising the
temperature or changing the solvent. With this SN1 reaction, which is very sensitive to
the polarity of the solvent, our technique is to place a sample in an equal volume of
water. This causes about a 10-fold increase in rate and permits the infinity value to be
measured after about one hour.

Procedure:
Prepare 60 mL of a 1:1 (by volume) solution of distilled water and 2-propanol.
Be as precise as possible. After mixing well, transfer the solution to a beaker and wait
10-15 minutes to allow the contents to come to room temperature as some heat will
evolve during the mixing of the two liquids.
Obtain ~50 mL of 0.05M NaOH and put it in the small plastic storage bottle. Set
up a 10 mL buret, rinse the buret with a little of the NaOH solution and then fill the buret
to the 0.00 mark with the NaOH solution.
In a 50.0 mL volumetric flask, weigh accurately a 0.500 g ± 0.020 g sample of
tert-butyl chloride. Add the water:isopropanol solvent to the mark of the volumetric
flask. Mix the contents well by inverting the flask several times. Note the time. This is
the starting time for the reaction. Transfer the contents to a 125 mL plastic bottle and put
the lid on.
The first sample should be taken out 10 minutes after the reaction is started.
Subsequent samples should be withdrawn at about 20, 35, 50, 65, and 85 minutes after
the start of the reaction. For each sample, a 5 mL aliquot is drawn into a 5 mL
volumetric pipet and transferred to a 50 mL Erlenmeyer flask containing about 5 mL of
acetone (the quench). Record the time of the addition. Add two drops of indicator
(bromothymol blue). The solution should be a faint yellow color. Titrate to a green end
point that persists for about 20 seconds. If the color stays blue, you have added too much
base. Record the volume of the base added. It is a good practice to continue titrating
until the solution turns blue although you don’t need to record the point when it turns
blue.
** The first titration should only take about 1-3 mL of base. If the titration is out of this
range, consult the instructor before proceeding.
To determine the infinity titer, a 5 mL sample from the solvolysis reaction is
added (using the volumetric pipet) to 5 mL of water. This sample may be titrated after
one hour. You may perform this step at any point during the reaction, but sooner is
better. Be sure an titrate the whole 10 mL mixture.

Now, generate a data table that shows the times and the amount of titer (base)
added for each sample. From this data, prepare a plot of log10(milliliters of titerinf –
milliliters of titer at time t) on the y-axis and time on the x-axis. It is a good idea to
sketch a rough graph during the laboratory to verify the quality of you data, but you need
to use a computer graphing program to perform a linear fit to the data and calculate the
value of the rate constant, k, in your final report.

Your write-up for this lab should include:


1. The electron-pushing mechanism for the solvolysis reaction
a. Explain why this reaction occurs as an SN1 reaction and not SN2
b. Identify the rate determining step and explain why it takes “so long”
2. A data table for the milliliters of titer and time of sample quenching
a. Explain the rationale behind quenching
b. Explain why the titerinf didn’t take an infinite amount of time
3. A graph of the log10(titerinf – titert) vs time
a. Add the trendline and show the equation as well as the correlation
factor (R2)
b. Calculate the rate constant (you don’t need to show the calculation
steps)
c. Discuss your graph (the correlation factor, problematic data points,
etc.)

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