EXPERIMENT 6 – STUDYING SN1 AND SN2 REACTIONS

This experiment should be performed in pairs and submitted individually at the end
of the lab period.

Prelab Assignment:

- Read and understand the procedure for Experiment 6 and prepare a flow chart.
- Read and understand the Operation 3 from the Laboratory Operations.
- Complete the prelab questions for this experiment.
- Complete the objective and the table of structures and physical properties on the report
sheet of this experiment. Include your references.

Introduction:

Substitution reactions, in which one atom or group of atoms replaces another, are
commonly observed for organic compounds. Many substitution reactions involve a
nucleophile – a species that contains an unshared pair of electrons that reacts with a site
in an organic molecule that has a deficiency of electrons. Nucleophilic substitution
reactions may occur by one of the two common mechanisms, designated SN1 and SN2.
The SN2 mechanism derives its designation from the fact the two chemical
species – the organic reactant and the nucleophile – participate in the rate determining
step of the reaction. The mechanism has only one step as illustrated below:

Some factors that can have a significant effect on the rate of the SN2 reaction
include:
(1) The leaving group: leaving groups are weak bases. The presence of a good
leaving group in the organic compound is essential for a nucleophilic substitution to
occur.
(2) The carbon group: an SN2 reaction occurs faster when the approach of the
nucleophile to the carbon is unhindered by the presence of bulky groups. For example,
the reaction occurs faster at primary carbon atoms than at secondary.
(3) The nucleophile: for nucleophiles in which the attacking species are of
comparable size, nucleophilicity parallels basicity. That is, stronger bases are better
nucleophiles than weaker bases. When nucleophiles differ in size, however, the larger,
more polarizable species are more nucleophilic, even though they are weaker bases.
(4) The solvent: reactions involving negatively charged nucleophiles occur much
more rapidly in polar aprotic solvents; that is solvents in which anionic nucleophiles are
poorly solvated.

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 (5) The concentration: higher concentrations of reactants involved in the rate-
determining step will increase the rate of reaction.

Nucleophilic substitution reactions may occur via an SN1 mechanism, in which

only the reactant is involved in the rate determining step, as shown below. The
nucleophile reacts in the fast step.

slow :Nu-H -H+

C L C C Nu
fast C Nu
fast
H

SN1 reactions occur when conditions favour ionization of the organic reactant.
Such conditions include:
(1) The leaving group: the leaving group must be a weak base.
(2) The carbon group: the rate determining step involves production of a
carbocation. This step will occur faster for those compounds that yield more stable
carbocations. For example, tertiary compounds react faster than secondary compounds.
Primary compounds react extremely slowly. Carbocation intermediates are also stabilized
by dispersal of the positive charge through delocalisation of electrons. SN1 reactions that
produce such resonance stabilized carbocation intermediates are also quite fast. For
example, SN1 reactions occur readily with molecules that form an allyl or a benzyl
carbocation.
(3) The solvent: ionization processes are facilitated by polar solvents. Because
the rate of an SN1 reaction is directly dependent on such ionization, the reaction occurs
much faster in polar solvents.
(4) The concentration: higher concentrations of reactants involved in the rate-
determining step will increase the rate of reaction.

Preview:

A. Factors affecting SN2 reactivity

 Prepare six test tubes containing a 15% solution of sodium iodide in anhydrous
acetone. One tube will be used as a comparison control.
 Add the indicated number of drops of the liquid to be tested to each test tube.
 Note the time required for a precipitate to appear.

B. Factors affecting SN1 reactivity

i) Measuring the effect of the leaving group on reaction rate

ii) Measuring the effect of alkyl group structure on reaction rate

iii) Measuring the effect of concentration on reaction rate

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 For i, ii and iii from above:
 Prepare a 50% 2-propanol / water mixture and add 25-mL portions of this solvent
to 5 flasks.
 Add indicator and NaOH solution to each.
 Add the indicated number of drops of alkyl halide and record the time needed for
discharge of the indicator colour.

iv) Measuring the effect of solvent polarity on reaction rate

 Prepare 40% and 60% 2-propanol / water solvent mixtures.
 Add indicator and NaOH solution to each.
 Add 2-bromo-2-methylpropane and measure the time required for discharge of the
indicator colour.

Chemical alert:
Alkyl halides Toxic and flammable. Avoid breathing any fumes.
Sodium iodide Skin and eye irritation.
Acetone Toxic, irritating and flammable.
2-propanol Highly flammable. Eye and respiratory irritation.
Sodium hydroxide Corrosive.
Phenolphthalein Flammable. Eye irritation.

Prevent eye, skin and clothing contact with all chemicals.

Procedure:

A. Factors affecting SN2 reactivity

USE SCRUPULOUSLY DRY TEST TUBES FOR THIS EXPERIMENT.

In a test tube containing 1 mL of a 15% solution of sodium iodide in anhydrous acetone,

add the required number of drops of the compound to be tested from the designated fume
hood according to the table on the next page. Cork the test tubes. Mix the contents by
gently shaking the tube. Record the time needed for a precipitate to form. If a precipitate
does not form within 15 minutes, stop observing and record the time as > 15 min.

The test tube containing only the sodium iodide acetone solution serves as a comparison
control.

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 TEST TUBE Solvent Alkyl Halide

15% NaI in anhydrous acetone 1-bromobutane

#1
1 mL 1 drop

15% NaI in anhydrous acetone 2-bromobutane

#2
1 mL 1 drop

15% NaI in anhydrous acetone 2-bromobutane

#3
1 mL 8 drops

15% NaI in anhydrous acetone 3-bromopropene

#4
1 mL 1 drop

15% NaI in anhydrous acetone Bromobenzene

#5
1 mL 1 drop

15% NaI in anhydrous acetone None

#6
1 mL (Control)

ALL SOLUTIONS FROM TEST TUBES MUST BE DISPOSED OF IN THE LIQUID

WASTE CONTAINER IN THE FUME HOOD.

ALL GLASSWARE MUST BE RINSED TWICE IN FUME HOOD WASTE

CONTAINER BEFORE WASHING.

Wash all equipment with soap, brush and hot water at the sinks at the periphery of the labs.

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B. Factors affecting SN1 reactivity

i), ii) & iii) Measuring the effect of the leaving group, the effect of the alkyl group
structure, and the effect of concentration on reaction rate
Prepare a 50% mixture of 2-propanol in distilled water by measuring 65 mL of 2-
propanol into a 150 mL beaker and pouring 65 mL of distilled water to make 130 mL
solution. Mix well.

Into each of the five 125 mL Erlenmeyer flasks, add the 2-propanol mixture, 0.5 M
NaOH, and phenolphthalein according to the table below. Add a magnetic stir bar to the
first three flasks, then cork and mix well. This basic solution should be bright pink. Note
that you cannot test more than three flasks at a time.

Next, at the designated fume hood, add the halides to the first three flasks according to
the table below and re-cork the flasks. At your bench, place the three flasks on a stir plate
at a dial setting of 4. Ensure the solutions are being mixed on the stir plate, and record the
time required for the solution to become colourless. If the solution does not become
colourless within 15 minutes, stop observing and record the time as > 15 min.

Repeat all necessary steps for the remaining flasks, ensuring that you clean the stir bars
before reusing them.

FLASK Alcohol Mixture Indicator Nucleophile Halide

2-bromo-2-
50% 2-propanol phenolphthalein 0.5 M NaOH
#1 methylpropane
25 mL 5 drops 5 drops
2 drops

2-chloro-2-
50% 2-propanol phenolphthalein 0.5 M NaOH
#2 methylpropane
25 mL 5 drops 5 drops
2 drops

2-chloro-2-
50% 2-propanol phenolphthalein 0.5 M NaOH
#3 methylpropane
25 mL 5 drops 5 drops
6 drops

50% 2-propanol phenolphthalein 0.5 M NaOH 2-bromopropane

#4
25 mL 5 drops 5 drops 2 drops

50% 2-propanol phenolphthalein 0.5 M NaOH 2-bromopropane

#5
25 mL 5 drops 5 drops 6 drops

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iv) Measuring the effect of solvent polarity on reaction rate

Prepare 50 mL of a 40% mixture of 2-propanol in distilled water by measuring 20 mL of

2-propanol into a 100-mL beaker and adding enough water to make 50 mL solution.
Transfer the mixture into a labelled 125-mL Erlenmeyer flask.

Prepare 50 mL of a 60% mixture of 2-propanol in water by measuring 30 mL of 2-

propanol into a 100-mL beaker and adding enough water to make 50 mL solution.
Transfer the mixture into a labelled 125-mL Erlenmeyer flask.

According to the table below, add phenolphthalein indicator and 0.5 M NaOH to each of
the flasks. Add a magnetic stir bar, then cork and mix well.

Add the halide in the designated fume hood, and re-cork the flask. At your bench, place
the flasks on a stir plate at a dial setting of 4. Ensure the solutions are being mixed on the
stir plate, and record the time required for the solution to become colourless.

FLASK Alcohol Mixture Indicator Nucleophile Halide

2-bromo-2-
40 % 2-propanol phenolphthalein 0.5 M NaOH
#1 methylpropane
50 mL 5 drops 5 drops
2 drops

2-bromo-2-
60 % 2-propanol phenolphthalein 0.5 M NaOH
#2 methylpropane
50 mL 5 drops 5 drops
2 drops

ALL SOLUTIONS FROM THE ERLENMEYER FLASKS MUST BE DISPOSED OF

IN THE LIQUID WASTE CONTAINER IN THE FUME HOOD.

ALL GLASSWARE MUST BE RINSED WITH ACETONE IN THE FUME HOOD

WASTE CONTAINER BEFORE WASHING.

Wash all equipment with soap, brush and hot water at the sinks at the periphery of the labs.

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REPORT SHEET – EXPERIMENT 6

Name: _________________________Section:________________Date:______________

Pre-lab questions:
1. Why must the acetone be anhydrous and the test tubes scrupulously dry for the test
with sodium iodide?

2. Which of the two solvent mixtures, 40% 2-propanol or 60% 2-propanol, is more polar?
Briefly explain.

3. How does the SN1 reaction in this experiment cause the acid-base indicator
phenolphthalein, to change colour? Briefly explain.

4. Which is a stronger base, Cl- or Br-?

5. Define what a cloudy or turbid solution means.

6. What is the precipitate formed when 1-bromobutane reacts with NaI in anhydrous
acetone?

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6-8
REPORT SHEET – EXPERIMENT 6

Name: _________________________Section:________________Date:______________

Objective:

A. Factors affecting SN2 reactivity.

Structure of Hazards of reactant Predicted Time to

reactant: R-Br structure of precipitate
(R group) product
1 drop
1-bromobutane
(1-butyl)

1 drop

2-bromobutane
(2-butyl)

8 drops

1 drop
3-bromopropene
(Allyl)

1 drop
bromobenzene
(Phenyl)

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 Compound Hazards
NaI

Acetone

1. Which alkyl halide, 1-bromobutane or 2-bromobutane, gave a higher rate of reaction

with I‒? Briefly explain.

2. What effect did increasing the concentration have on the reaction times for the 2-
bromobutane? Briefly explain.

B. Factors affecting SN1 reactivity

i), ii), & iii) Measuring the effect of the leaving group, the effect of the alkyl group
structure, and the effect of concentration on reaction rate
Structure of alkyl halide Hazards of reactant Predicted structure Time for
of product discolouration
2-bromo-2-methylpropane 2 drops

2-chloro-2-methylpropane 2 drops

6 drops

2-bromopropane 2 drops

6 drops

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 Compound Hazards

2-propanol

NaOH

Phenolphthalein

1. When comparing the tertiary alkyl halides, which is a better leaving group, Br‒ or Cl‒?
Are these results consistent with the relative basicities of these two ions? Briefly explain.

2. How are the reactivities of 2-bromo-2-methylpropane and 2-bromopropane related to

the stabilities of the carbocations produced as intermediates in the reaction? Briefly
explain.

3. What effect did increasing the concentration have on the reaction times for the 2-
chloro-2-methylpropane and the 2-bromopropane? Briefly explain.

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 iv) Measuring the effect of solvent polarity on reaction rate

Structure of alkyl halide Solvent Time for discolouration

2-bromo-2-
methylpropane 40 % 2-propanol

60 % 2-propanol

1. In which of the two solvent mixtures did 2-bromo-2-methylpropane react faster?

Explain your results in terms of the effect of solvent polarity on the rate determining step
in the SN1 reaction.

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