CHEM

2020

Kinetics of Nucleophilic
Substitutions
EXPERIMENT 4 SEMIFORMAL LAB REPORT
SULAIMAAN BHATTI 215947823 PARTNER: RAJ CHETTIAR
1. Determine the effect of varying [OH- ] on the rate of the reaction. To do this, you should
complete the following table:

Experiment [tBuCl] [OH-] Reaction Time Reaction Rate Rate Constant k

(M) (M) (s) (M/s) (s-1)

1 0.03 0.003 59.37 1.16 × 10-4 3.88 × 10-2

2 0.03 0.006 121.13 3.99 × 10-4 1.33 × 10-2

3 0.03 0.009 187.08 1.93 × 10-4 6.44 × 10-3

Be sure to calculate the starting concentrations of tBuCl and OHcarefully. To calculate the
reaction rate, remember that the concentration of tBuCl that has reacted in the recorded time is
= [OH- ] for that experiment

(3 mL × 0.1 mol/L)
[tBuCl] = C2 = C1V1 /V2 = = 0.03 M
10 mL
[OH−] = 10% of 0.03M = 0.003 M
1 1
Rate constant: 𝑘𝑡 = ln 1−𝑋 = ln 1−0.9
𝑡
Reaction rate: k[tBuCl] = 3.88 x 10−2 (0.03)

What is the dependence of [OH- ] on the rate law?

Because the reaction rate is very similar across the three trials, the concentration of hydroxide
ions appears to be independent of the rate law. This was also addressed in the prelab, where
the role of hydroxide was only to stabilize carbocation, and act as a protic solvent in this Sn1
reaction.
2. Determine the effect of varying [tBuCl] on the reaction rate. Completing the following table
will assist you.

Experiment [tBuCl] [OH-] Reaction Time Reaction Rate Rate Constant k

(M) (M) (s) (M/s) (s-1)

4 0.06 0.003 33.33 5.39 × 10-3 8.99 × 10-2

1 0.03 0.003 59.37 1.16 × 10-4 3.88 × 10-2

5 0.015 0.003 61.41 3.93 × 10-4 2.62 × 10-2

*Uses same equations as question 1

What is the dependence of [tBuCl] on the rate law?

5.39 x 10−3 = 8.99 × 10−2 (0.06) α

𝑂𝑟𝑑𝑒𝑟 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛:
3.93 x 10−4 = 2.62 × 10−2 (0.015) α

0.000002118 = (0.000002118)A
A=1

Based on these calculations, the dependence of [tBuCl] on the rate law is first order. This makes
it the rate-determining-step because the first step had no effect on rate. We also know this
reaction is a first order reaction.

3. Based on the experimental rate law, what mechanism(s) do you think are happening in the
solvolysis reaction of tBuCl? What product(s) do you predict for this reaction (draw the reaction
mechanisms and product structures)?
4. Calculate the activation energy (Ea) for this reaction. To do this, you need to construct an
Arrhenius plot. First, complete the following table.

Experiment Temp (K) Reaction Time (s) Reaction Rate (M/s) Rate Constant k (s-1)

1 292.65 59.37 1.16 × 10-4 3.88 × 10-2

6, trial 1 282.65 269.86 1.71 × 1046 8.53 × 10-3

6, trial 2 282.15 254.44 1.81 × 10-4 9.05 × 10-3

7, trial 1 302.65 28.07 4.68 × 10-3 1.17 × 10-1

7, trial 2 303.65 25.09 5.24 × 10-3 1.31 × 10-1

Calculate the reaction rate using the same method you used above. To calculate the rate
constant k, use the experimental rate law: Reaction rate = k[tBuCl]m[OH- ] n where m and n
were determined earlier in this report.

Construct an Arrhenius plot by making a graph (using Excel or any other graphing software) of
ln k vs. 1/T which should give a straight line. Determine the slope and y-intercept of the line of
best fit and include a copy of your plot in your report. Using the slope and intercept values,
calculate the activation energy (Ea), using the appropriate equation in the lab manual. Watch
your units!

0
Arrhenius Plot: Solvolysis of tBuCl
0.00325 0.0033 0.00335 0.0034 0.00345 0.0035 0.00355 0.0036
-1

-2
ln K

-3

-4
y = -5549.3x + 15.489

-5

-6
1/T

Slope of line of best fit= 5549.3 mol•K

Slope =Ea / 2.303R
Ea= (5549.3)(8.314) =46136.88 J = 46.14 kJ
Explain clearly the effect of temperature on the reaction rate, making reference to the activation
energy value you obtained.

As temperature increases, so does the rate of the reaction. Temperature has a big impact
because the time increased by 5x through a 10-degree lowering, and took half the time when
increased by 10 degrees. The reaction rate clearly increases when increased temperature
allows the kinetic energy of the molecules to exceed the activation energy of 46.14 kJ more
efficiently.

5. Comment on how the reaction rate constant (not the rate) varied when you adjusted the
solvent composition, making reference to the mechanism(s) you proposed in question 3.

Because this reaction occurs through an SN1 mechanism, it greatly prefers protic solvents, such
as water, instead of aprotic solvents like acetone. This is supported in the experiment because the
80:20 composition reacted significantly faster than the 60:40 mix of water-to-acetone.

6. Comment on how the reaction rate may vary if a different substrate such as 2-chloropropane
(iPrCl) was used. Justify your answer by making reference to the mechanism(s) you proposed in
question 3.

iPrCl is a less bulky compound compared to our tBuCl. The stereochemistry shows that only a
secondary carbocation could be formed. Secondary carbocations are less stable, and will likely
require a greater activation energy. This may lead to the reaction not occurring at all, or
occurring at an extremely slow rate.

7. In this experiment you used relatively low concentrations of OH- . If [OH- ] was increased,
only one product should be observed upon reaction with tBuCl. What mechanism do you think
would occur? Draw the structure of the predicted product based on the mechanism you
proposed.

If we increased the concentration of hydroxide ions to a significant amount, it would cause an

E2 reaction. SN2 will not occur because the reaction must form a tertiary carbocation. This type
of elimination reaction can occur because hydroxide is a strong base. This reaction will result in
isobutene, the alkene being formed.