Dehydration of Cyclohexanol

CHEM 0345, Mondays 6:00-10:00 PM, Sam Kavoosi

Michael Hensler*
Kevin Dou

Date Performed: October 3, 2016

1
 1.0 Experimental Goal

The goal of this experiment was to form cyclohexene through the E1 elimination of
cyclohexanol. To separate and purify the cyclohexene, a simple distillation was utilized. A
separatory funnel was then used to remove any impurities that may have distilled into the
cyclohexene solution. To determine whether or not the alkene formed, a bromine test was
conducted. Infrared (IR) spectroscopy was performed to allow for further analysis of the various
bond types in the cyclohexene.

2.0 Experimental Outline

Figure 1: Overall Reaction for the Dehydration of Cyclohexanol

Table 1: Reactant and Product Values and Properties1

Compound MW Density (g/mL) Amount Moles (mol) MP/BP (°C)
(g/mol)
Cyclohexanol 100.159 0.9624 10.0 mL 0.09609 25.93/160.8
Phosphoric acid 97.995 1.834 12.0 mL 0.2246 42.35/158
Cyclohexene 82.1436 0.8110 4.79 g 0.0583 -103.5/83

Figure 2: Reaction Mechanism of Cyclohexanol to Cyclohexene

2
 3.0 Experimental
To 10 mL of cyclohexanol was added 12 mL of 85% phosphoric acid and a few black
charcoal boiling chips into a 100 mL round bottom flask. A simple distillation apparatus was set
up with the reactor flask, securely fastened to the monkey bars, placed on a heating mantle on a
raised lab jack. A 50 mL round bottom flask was immersed in an ice-water bath to receive the
products. The thermometer was monitored such that the temperature of the reactor flask did not
exceed 100°C. The steady-state temperature was recorded. Once about 10 mL of the liquid was
left in the reactor, the lab jack was lowered, and the products were transferred to a separatory
funnel. The products remaining in the receiver flask were rinsed with approximately 2 mL of
10% Na2CO3 (aq). This solution was transferred to the separatory funnel and to the separatory
funnel was added an additional 3 mL of 10% Na2CO3 (aq). The funnel was vented and swirled
several times, and the aqueous layer was drained. To the remaining liquid was added two
portions of 10 mL saturated NaCl solution. The organic liquid was drained into a 25 mL
Erlenmeyer flask and dried over anhydrous Na2SO4 (s). Into a pre-weighed flask was decanted the
liquid. The mass of the liquid in the flask was recorded. A small amount of the liquid was
transferred to a test tube, and a bromine test was conducted to test for the presence of an alkene.
Upon confirmation of the alkene, an IR spectroscopy was taken of the organic liquid.

4.0 Results
As the reaction took place, the contents in the reactor flask turned from clear to a yellow
color, then to a golden yellow, and finally to a golden brown. The products in the receiver flask
were clear. The temperature at which the vapor above the reaction flask stabilized was 82°C.
Both times that the separatory funnel was used, there were two distinguishable liquid layers that
formed. Both liquids were clear.
The weight of the beaker, round bottom flask, and stopper was 170.52 g. After the
organic product was decanted into this pre-weighed set, the total mass was found to be 175.31 g.
By subtracting these two masses, the yield of the cyclohexene from the experiment can be found
through equation (1).
Cyclohexene yield = mass of set and cyclohexene – mass of set
= 175.21 g – 170.52 g
= 4.79 g C6H10 (1)

3
 The theoretical yield of the cyclohexene is governed by equation (2).
0.962 𝑔 C6H12O 1 𝑚𝑜𝑙 C6H12O
Theoretical yield = 10.0 mL C6H12O 𝑥 𝑥 100.158 𝑔 C6H12O
1 𝑚𝐿
1 𝑚𝑜𝑙 𝐶6𝐻10 82.143 𝑔 𝐶6𝐻10
𝑥 1 𝑚𝑜𝑙 C6H12O 𝑥 1 𝑚𝑜𝑙 𝐶6𝐻10

= 7.89 g C6H10 (2)

As a result of equations (1) and (2), the percent yield from this experiment can be found
through equation (3).
𝐴𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑 4.79 𝑔 C6H10
% yield = 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑 𝑥 100% = 7.89 𝑔 C6H10 𝑥 100% = 60.7% (3)

When the Br2-H2O was added to the cyclohexene during the bromine test, the solution
turned from clear to orange, then to yellow, and then back to clear. The IR spectrum produced
three important peaks: one at 3062.22 cm-1, another at 1652.30 cm-1, and a third one between
3400-3500 cm-1. Additional IR data is attached to the end of this report.

5.0 Discussion
The reaction mixture was heated since elimination reactions are favored by heat.2 This
phenomenon can be shown through equation (4), which is the Gibb’s Free Energy equation.
∆G = ∆H - T∆S (4)
For the dehydration of cyclohexanol reaction, the process is endothermic (i.e. ∆H is positive) and
has more products than reactants (i.e. ∆S is positive). As a result, ∆G is positive at lower
temperatures, which means that the reaction is unfavorable, and ∆G is negative at higher
temperatures, which makes the reaction likely to happen.
The distillation of cyclohexene from the reaction mixture increases the percent
conversion of cyclohexanol to cyclohexene. The boiling point of cyclohexene is about 83°C and
the boiling point of cyclohexanol is about 162°C.1 Thus, by keeping the distillation temperature
at about 82°C, cyclohexene was able to boil out of solution while keeping cyclohexanol in the
reaction mixture. Additionally, Le Chatelier’s principle says that as the cyclohexene was
removed from the reactor flask via distillation, the equilibrium was pushed more towards the
products, which ensured additional cyclohexene was formed. Given that the percent conversion
in this experiment was only 60.7%, it is clear that not all of the cyclohexene boiled out of
solution. By allowing the reaction to take place for a longer period of time, the percent
conversion would have increased.

4
 The bromine test ensured that cyclohexene was produced in the experiment. After
inserting several drops of the Br2-H2O mixture, the orange-brown color from the bromine
dissipated as a result of the attack of the bromine on the double bond in cyclohexene. This
reaction produced the colorless trans-bromohydrin compound. Had no alkene been present, the
orange-brown bromine would not have been consumed and the brown hue would have remained
in solution.
The IR spectrum helped to distinguish the key components of a successful reaction. A
peak on the spectrum was recorded at 1652.30 cm-1, which is indicative of an alkene group being
present. Additionally, there was a medium-sized peak located at 3062.22 cm-1. This peak
corresponds to a hydrogen atom bonded to an sp2-hybridized carbon. These two peaks indicate
the successful formation of cyclohexene. There is, however, a small, broad peak around 3400-
3500 cm-1, which is indicative of a concentrated alcohol being present. This means that there was
potentially some cyclohexanol or even excess water impurities in the cylcohexene product.
The cyclohexanol NMR spectrum shows a peak at about 3.6 ppm and an integration
number of 0.12. The peak value and integration number correspond to a single alcohol hydrogen,
which has a literature peak between 0.5-5 ppm. The cyclohexene NMR spectrum shows a peak at
about 5.67 ppm and an integration number of 1.00, which is indicative of two alkene hydrogens
being present. The literature peak of alkene hydrogens occurs between 4.5-6 ppm.
If an NMR were to be obtained of the product from this experiment, then the product’s
spectrum could be compared to that of cyclohexene’s. If the product’s peaks occurred around
1.62 ppm, 1.98 ppm, and 5.67 ppm as cyclohexene’s are, then the reaction would be successful.
However, erroneous, broad peaks between 0.5 ppm and 5 ppm would indicate that cyclohexanol
was present and that the reaction was not a success.
The molar percent of cyclohexene in cyclohexene and cyclohexanol mixture is
determined by using the integration numbers on the NMR spectrum. Cyclohexanol, with a spike
around 3.5-3.6 ppm, has an integration number of 0.12 with one hydrogen. Thus, 0.12 moles of
cyclohexanol are present in the mixture. Cyclohexene, with a spike around 5.6 ppm, has an
integration number of 1.00 with two hydrogens. Thus, 0.5 moles of cyclohexene are in the
mixture. The molar percent of cyclohexene in the mixture can then be found through equation
(5).
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑐𝑦𝑐𝑙𝑜ℎ𝑒𝑥𝑒𝑛𝑒 0.5 𝑚𝑜𝑙𝑒𝑠
Molar % = 𝑥 100% = (0.5+0.12)𝑚𝑜𝑙𝑒𝑠 𝑥 100% = 80.65% (5)
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠

5
 6.0 References
1. National Library of Medicine. PubChem Compound.
https://www.ncbi.nlm.nih.gov/pccompound (accessed Oct 7, 2016).
2. James. Elimination Reactions Are Favored By Heat.
http://www.masterorganicchemistry.com/2012/09/10/elimination-reactions-are-favored-
by-heat/ (accessed Oct 8, 2016).