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Experiment 9:

Alkenes from Alcohols: Analysis of


a Mixture by Gas Chromatography
Introduction

This experiment focuses in the understanding of an elimination reaction. The elimination

reaction plays an important role in this experiment. In an elimination reaction, a halide ion leaves

with another atom or ion (Weldegirma, 2012). Elimination reactions have two mechanisms, E1

and E2. E1 reactions are unimolecular, meaning that the rate of the reaction depends only on the

concentration of the substrate. It has two steps. In the first step, the halogen leaves the molecule,

forming a carbocation. In the second step, the nucleophile extracts a proton from the molecule,

and a pi bond is formed. An E2 reaction is bimolecular, meaning that the rate of reaction depends

on the concentration of the substrate and the nucleophile (Comparing). In this reaction, the

leaving of the halogen, the extraction of the proton, and the formation of a pi bond occur

simultaneously in one step. The products of E1 and E2 reactions are substituted alkenes. Both

mechanisms are favored when there is heat, or a high temperature. Since the competition reaction

of an E1 reaction is the SN1 reaction, heat can favor the elimination reaction over the substitution

reaction. In substitution reactions, the nucleophile replaced a halogen atom in an alkyl halide. In

elimination reactions, the nucleophile acts as a base, meaning that it extracts a proton form the

alkyl halide. E1 reactions are favored when there is a weak nucleophile, such as water, methanol,

ethanol, isopropanol, etc. E2 reactions are favored when there is a strong nucleophile, such as the

hydroxide ion, cyanide ion, and thiol group.

Zaitsev's rule, based on the dehydration of alcohols, describes the preference for

eliminations to give the highly substituted (more stable) alkene, which may also be described as

the Zaitsev product (Elimination). As mentioned before, the product of an elimination reaction is

a substituted alkene. Alkenes can be monosubstituted, disubstituted, trisubstituted, or


tetrasubstituted. According to Zaitsev’s rule, the more substituted alkene will be the major

product. The minor product is also known as a Hoffmann product.

The purpose of this experiment is to dehydrate 2-methyl-2-butanol, using concentrated

sulfuric acid as a catalyst, to give a mixture of alkenes that can be analyzed by gas

chromatography. The mechanism of the synthesis of 2-methyl-1-butene and 2-methyl-2-butene is

shown in Figure 1., and the possible side reaction during the synthesis of the alkenes is shown in

Figure 2.

OH OH2
i. H

H
ii. H2O
Minor

H
H
H2O
Major

Figure 1. Mechanism of the synthesis of 2-methyl-1-butene and 2-methyl-2-butene.

OH
H2O

H
Figure 2. Possible reaction during the synthesis of the alkenes.
Experimental Section

10-mL conical flask

+ 1.5 mL of distilled water


+ boiling stones
+ 1 mL of concentrated sulfuric acid
+ ice bath
+ 2 mL of 2-methyl-2-butanol
+ swirl

Simple distillation

+ reflux slowly at 30-40 degrees Celsius


+ collect the oily butenes in a 10-mL collection vial
+ add CaCl2 pellets

Oily product

Gas Chromatography

Diagram 1. Summary of alcohol dehydration and gas chromatography.

This experiment consists of two parts: the first part is the dehydration of 2-methyl-2-

butanol to form a mixture of alkenes and the second part is the analysis of the alkenes by gas

chromatography. To begin with the first part, 1.50 mL of distilled water were added to a 10.0 mL

conical flask. A total volume od 1.00 mL of concentrated sulfuric acid was added drop wise to

the vial containing the water. The solution was mixed as the sulfuric acid was added. When the

sulfuric acid was added, the solution started to become very hot, so it was placed in an ice bath in

order for it to cool. After the solution was cooled, 2.00 mL of 2-methyl-2-butanol were added to

the vial. The solution was mixed thoroughly, and boiling stones were added to the vial. A simple

distillation apparatus was assembled in order to obtain the mixture of alkenes. The vial

containing the solution was accommodated in the distillation apparatus, a thermometer was
introduced to record the temperature, and the receiving flask was placed in an ice bath to avoid

the vaporization of the distillate. Pellets of calcium chloride were added to the receiving flask in

order to dry the distillate. The sand bath was heated until the temperature reached approximately

30 to 40 degrees Celsius. The solution started to boil and the distillate was collected in a pre-

weighed vial. The vial with the alkene mixture was weighed, and the mass of the alkene mixture

was calculated. The product was then examined by gas chromatography. A clean syringe was

used to take out 1.0 μL of the solution and place it in the injector. A chromatogram containing

data about the mixture was obtained and interpreted.

Table of Chemicals

Chemicals
Physical Properties 2-methyl-2-butanol 2-methyl-2-butene Sulfuric acid
Molar mass 88.15 g/mol 70.13 g/mol 98.079 g/mol
Melting point -9.0 °C -134 °C 10.0 °C
Vapor pressure 1.60 kPa 2.90 mmHg NA
(20 °C)
Boiling point 101-103 °C 39.0 °C 337 °C
Appearance Colorless liquid Colorless liquid Odorless, clear liquid
Density 805 mg/mL 0.662 g/mL 1.84 g/mL
Table 1. Physical properties of the chemicals used.

Chemicals
Chemical 2-methyl-2-butanol 2-methyl-2-butene Sulfuric acid
Properties
Solubility in water 120 g/dm3 Insoluble Miscible
Flammability Combustible Flammable Highly flammable
Reacts violently with Incompatible with Can react
Reactivity nitric acid, strong bases, strong exothermically with
incompatible with oxidizing agents, bases and diazo
sodium nitrite. alkalies. compounds.
Enthalpy of -380 kJ/mol NA -814 kJ/mol
formation
Table 2. Chemical properties of the chemicals used.
Results

Calculating percent yield of alkenes

Theoretical moles of alkene:

1 𝑚𝑜l C5 H12 O 1 𝑚𝑜𝑙 𝑎𝑙𝑘𝑒𝑛𝑒


0.46 𝑔 C5 H12 O × × = 0.00521 𝑚𝑜𝑙 𝑜𝑓 𝑎𝑙𝑘𝑒𝑛𝑒
88.15 𝑔 C5 H12 O 1 𝑚𝑜𝑙 C5 H12 O

Actual moles of alkene:

1 𝑚𝑜𝑙 𝑎𝑙𝑘𝑒𝑛𝑒
0.00521 𝑔 alkene × = 0.0000744 𝑚𝑜𝑙 𝑎𝑙𝑘𝑒𝑛𝑒
70.13 𝑔 𝑎𝑙𝑘𝑒𝑛𝑒

𝑎𝑐𝑡𝑢𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑙𝑘𝑒𝑛𝑒 0.0000744 𝑚𝑜𝑙


% 𝐲𝐢𝐞𝐥𝐝 = × 100% = × 100% = 1.43 %
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑙𝑘𝑒𝑛𝑒 0.00521 𝑚𝑜𝑙

The gas chromatogram:

Discussion

The gas chromatogram provides the retention time, height, area, and concentration of the

alkenes in the mixture. Based on the chromatogram, it can be observed that there is a major

concentration of one of the alkenes. There is a peak that has more area than the other. The peak

with the highest area belongs to 2-methyl-2-butene, and the peak with the lowest area belongs to

2-methyl-1-butene. The percentages of 2-methyl-1-butene and 2-methyl-2-butene in the mixture

are 12.36 % and 87.6%, respectively. The major product in this mixture is 2-methyl-2-butene.
The high concentration of this compound can help determine which is the major product. The

chromatogram shows that the highest peak corresponds to 2-methyl-2-butene, which means that

2-methyl-2-butene was the most abundant isomer in the mixture. Another reason why 2-methyl-

2-butene is the major product is because it is a more substituted alkene than 2-methyl-1-butene.

2-methyl-2-butene is a trisubstituted alkene, while 2-methyl-1-butene is a disubstituted alkene.

The percent yield for the alkenes was very low. During the reaction of 2-methyl-2-butanol

and sulfuric acid, some of the undesired product could have formed, which is the 2-methyl-2-

butanol. This side reaction could have yielded a lower amount of alkenes compared to the

theoretical value. Another possible explanation for the low percent yield might be that some of

the distillate could have evaporated, since the mixture was very volatile. This could have caused

a partial loss of the alkene mixture.

Conclusion

The information of the data has revealed that there was a higher concentration of 2-methyl-

2-butene than 2-methyl-1-butene. This demonstrates the fact that a more substituted alkene is the

major product of an elimination reaction. By dehydrating an alcohol to yield a mixture of alkenes

and analyzing the mixture by gas chromatography, the relative amounts of the compounds can be

determined. It can also be used to verify which of the compounds in the mixture is the major

product. Side reactions and other factors can affect the overall results of the experiment. The

technique of gas chromatography can be used to analyze mixtures of different types of alkenes.

Different alcohols can be dehydrated to form different alkenes. The lab accomplished what it set

out to do.
References

Comparing the E1 and E2 Reactions. Master Organic Chemistry.

http://www.masterorganicchemistry.com/2012/10/10/comparing-the-e1-and-e2-reactions/

(accessed March 2014).

Elimination Reactions.

http://www.mhhe.com/physsci/chemistry/carey/student/olc/graphics/carey04oc/ref/ch05el

iminationreactions.html (accessed March 2014).

Weldegirma, S. Experimental Organic Chemistry; Cengage Learning: Ohio, 2012; p 38.

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