University of Research and Technological Investigation

“YACHAY TECH”

School of Chemical Sciences and Engineering

ORGANIC CHEMISTRY I

PRACTICE 5:
NUCLEOPHILIC SUBSTITUTION

Authors:
Luzuriaga Espinoza Kenia Michelle
Palma Loor María Daniela

Professor:
Hortensia Rodriguez, Ph.D.

Date:
8 - Jun - 2021

SEMESTER I - 2021
❖OBJECTIVES
● To demonstrate in the laboratory setting Nucleophilic substitution reactions of
alkyl halides. In this experiment, a nucleophilic substitution reaction will be
represented by the addition of a solvent to mixtures of alkyl halides. Any change
will be noted and represents a reaction.

❖INTRODUCTION
Nucleophilic substitution is one of the most valuable and well-studied classes of
organic reactions. These reactions can occur by a variety of mechanisms. SN2 and
SN1 are the reactions in question. In this experiment SN2 reaction occurs in a single
step but the overall procedure did not differ. The process goes as follows, the
nucleophile enters as the leaving group which usually is a halide ion and it departs.
The reaction in the experiment has a rate that is proportional to the concentration
of the solvents used and the nucleophile in question. In the SN1 reaction loss of the
“leaving group” occurs first to generate a carbocation intermediate. The
carbocation then takes a nucleophile, often the solvent In this case the reaction is
called solvolysis. Since the first step is rate-determining in an SN1 reaction it
displays first-order kinetics and its rate depends only on the concentration of the
halide used. Which mechanism occurs under a certain set of conditions and how
fast it occurs depend on a variety of factors. These factors include structure, the
available leaving group, the nucleophile being tested, and the solvent use all play a
role in the reaction that takes place. The objective of this laboratory experiment is
to learn how variations in halide structure affect the rates of SN1 and SN2 reactions.
Within this experiment, a main part of the procedure is measuring reaction rates.
This involves monitoring the rate of change of the products during the experiment.
In this experiment, it is important to determine reaction rates by measuring the
time required for a visible change to occur. The most common physical change is the
formation of a precipitate. To create an SN2 reaction mechanism in the laboratory a
solution of NaI in acetone will be used. Iodide is a good nucleophile, and if it
displaces bromide or chloride, NaBr or NaCl it is known to precipitate (Organic
Experiments 2010). To emulate an SN1 reaction mechanism AgNO3 in ethanol will
be used. Ethanol is used as it is a polar protic solvent and can promote the
ionization of certain halides used in the experiment.
If a halide ion is released a precipitate of AgCl or Gab will form in the experiment.
Overall our procedure included using test tubes. For the SN1 reaction 1ml of alkyl
halides will be used with an addition of 1ml of ethanoic AGNO3. For SN2 the
procedure is similar except 0.1ml of alkyl halides is used, and 1ml of NaI is used. The
procedure then remains the same and observed for reaction while wax stoppers are
used to prevent spilling.
❖DATA & CALCULATION
Scheme 1: General Reaction first part

In part one, we will study the SN1 reaction using 11 test tube reactions. All reactions
have the same general reaction.
Then, In three of the test tube reactions, how the alkyl halide structure plays a role in
the rate of the reactions will be tested. Three different alkyl chlorides under the same
conditions will be tested

In two of the test tube reactions, the solven polarity effects on the reaction will be
tested. Two different solvents will be tested:
 Test tube Solvent Type of solvent

1 100% Ethanol Polar protic

2 5% Etanol: 95% acetone Mostly polar aprotic

In two of the test tube reactions, the leaving group effects will be tested. Two different
alkyl halides will be used:

Scheme 2. General Reaction second Part

In part two, we will study the SN2 reaction using 11 test tube reactions. All reactions
have the same general reaction. In three of the test tube reactions, how the alkyl
halide structure plays a role in the rate of the reactions will be tested. This will
compare the steric effects of the carbon that is bound to the bromine. Three different
alkyl chlorides under the same conditions will be tested.

In two of the test tube reactions, the secondary steric effects of the alkyl halide will be
tested. These are steric effects on the molecule, not including the carbon bound to
bromide. Two different primary alkyl bromides, under the same conditions, will be
tested

In two of the test tube reactions, the leaving group effects will be tested. Two different
alkyl halides will be used:
❖SAFETY DATASHEET
❖MATERIALS
❖ Test Tubes
❖ Micro Pipettes
❖ Stop-Watch
❖ Temporary Labels

❖REAGENTS
● 2 mL of a 0.1 M solution of silver nitrate in ethanol
● 2 drops of 1‐bromobutane
● 2 drops of 2‐bromobutane
● 2 drops of 2‐bromo‐2‐methylpropane
● 2 drops of 2‐chloro‐2‐ methylpropane
● 0.1 M solution of silver nitrate in 5% ethanol/95% acetone
● 0.5 mL of a 0.1 M solution of 2‐chloro‐2‐methylpropane
● 0.5 mL of a 0.2 M solution of 2‐chloro‐2‐methylpropane in etanol
● 2 mL of 15% sodium iodide in acetone
● 2 drops of neopentyl bromide
● 2 drops of 1‐chlorobutane
● 1.0 M solution of 1‐bromobutane in acetone
● 0.1 mL of a 2.0 M solution of 1‐bromobutane in acetone
❖PROCEDURE

Part 1: Studying SN1 Reactions

1.1. Alkyl Halide Structure:

1.2. Leaving Group Effects:

1.3. Solvent Polarity Effects:

1.4. Determining the SN1 Rate Law:

Part 2: Studying SN2 Reactions

2.1. Alkyl Halide Structure:

2.2. Steric Effects:

2.3. Leaving Group Effects:

2.4. Determining the SN2 Rate Law:

Remember:

In a nucleophilic substitution, the nucleophile reacts with the alkyl halide by attacking
the electrophile alpha carbon. The nucleophile acts as a Lewis base, donating a pair of
electrons to the alpha carbon. Meanwhile, the bond between the alpha carbon and the
halogen is broken. The electrons originally in this bond join with the halogen to form a
halide leaving group.

OBSERVATIONS
Nucleophilic Substitution
❖RESULTS
Part 1: Studying SN1 Reactions

Alkyl Halide Structure:

Leaving Group Effects:

Solvent Polarity Effects:

Determining the SN1 Rate Law:

Test Tube Silver nitrate 1-Bromobutane Time until precipitation

Concentration Concentration

1 0.1 M 0.1 M 20 s

2 0.1 M 0.2 M 10 s

3 0.1 M 0.1 M 20 s

4 0.05 M 0.1 M 20 s

Part 2: Studying SN2 Reactions

Alkyl Halide Structure:

Steric Effects:

Leaving Group Effects:

Determining the SN2 Rate Law:

Test Tube Sodium iodide 1-Bromobutane Time until precipitation

Concentration Concentration

1 15% 1.0 M 20 s

2 15% 2.0 M 10 s

3 15% 1.0 M 20 s

4 75% 1.0 M 40 s
❖CONCLUSION
● Alkyl halides can react with Sn2 or Sn1 mechanisms. Sn2 requires a good
nucleophile (like I-) and a polar aprotic solvent like acetone. Primary and
Secondary halides react well with Sn2 but not tertiary because of steric
hindrance. Sn1 requires a weaker nucleophile such as ethanol, and a promoter
of carbocation formation such as Ag+. Tertiary and Secondary halides react best
with Sn1 but not primary halides that are unless rearrangement can
simultaneously occur.

❖REFERENCES
● Organic Chemistry, 2nd Edition by J. Clayden, N. Greeves, S. Warren. Oxford
University Press. 2012
● Williamson, Kenneth L. Organic Experiments. Vol. 9, Cengage Learning, 2011.
● Morrison, Robert Thornton., et al. Organic Chemistry. Pearson, 2011