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Dehydration of an Alcohol

Required Reading: Mayo, pg 134; Wade section 7-10 page 306.

Background:
Dehydration is an acid catalyzed elimination reaction involving the loss of H2O
from an alcohol to produce an alkene. The mechanism of the dehydration reaction is
given for 2-butanol in Wade pg 307-308. The first step in the reaction is the protonation
of the alcohol, an acid-base step:
H H
HO O O O
H O S O H + O S O H
O O

From this point on, the reaction is an E-1 elimination involving a carbocation
intermediate. In the second step, H2O is separated from the substrate to form a
carbocation:
H H
O
+ H2O

Characteristic of any carbocation, this intermediate may rearrange if there is a possibility


of forming a more stable carbocation. The final step in the elimination process is the loss
of a proton from the carbon adjacent to the C+. This is another acid-base reaction. The
proton is returned to restore the catalyst (or passed to another alcohol molecule to begin a
new dehydration cycle). Note that the electron pair which bonded this proton to carbon,
becomes the  bond of the alkene:

O + H3O+
H H
H

In the laboratory, you will be dehydrating either 1-butanol or 2-butanol and


measuring the relative amounts of 1-butene, cis-2-butene and trans-2-butene formed. In
addition, you will interpret the data to determine the ratio of rates (and the difference in
the activation energies) of two alternative reactions of the 1-butyl carbocation.

Procedure:
You will work in teams of two, however one member of the team will dehydrate
1-butanol and the other member will dehydrate 2-butanol. Therefore, everyone will
individually perform a dehydration.

***** As soon as you walk into the lab, prepare, and begin to warm *****
your sand bath. Turn the heat to a moderate setting (12:00
position). As your instructor is giving the pre-lab discussion
and quiz, the sand bath will warm, saving valuable time.

Dehydration of an Alcohol 85
To a 3 mL conical vial with a magnetic spin vane or micro-stirbar, add 0.30 mL of
the alcohol (either 1-butanol or 2-butanol), and 4 drops of concentrated H2SO4.
Extreme caution must be exercised with concentrated sulfuric acid!
It is very corrosive, especially to human tissue. If you spill even
one drop, you must immediately wipe it up with a damp paper
towel. If you spill some on your skin, immediately rinse the
affected area with copious amounts of water in the sink. If the
outside of the bottle appears wet, assume it is H2SO4 and take
precaution.

Place the air condenser, with an o-ring and cap on the vial. To the top of the air
condenser, attach the capillary gas delivery tube, with an o-ring and cap. The apparatus
is shown below (Figure 1).

(a)

(c)
(d)
(b)
(e)

Figure 1. Dehydration of an alcohol gas collection apparatus


(a) capillary gas delivery tube
(b) air condenser
(c) U-portion of capillary gas delivery tube
(d) wire gauze
(e) iron ring

Clamp the apparatus to a ring stand, but do not yet lower it into the sand bath.
Clamp an iron ring to the ring stand (Figure 1e) and place a square of wire gauze (Figure
1 d) over the iron ring. This will serve as a platform to place a beaker where the gas
collection will occur. Arrange the iron ring so that it is positioned ~1 inch under the U-
portion of the capillary gas delivery tube (Figure 1c). Also make sure the U-portion of
the delivery tube is centered over the iron ring. You may need to manipulate the angles
of both the iron ring and delivery tube for this to occur. Lower the vial, condenser and
delivery tube until the conical vial is buried in the sand bath (push the vial all the way to
the bottom of the sand bath). You may also need to simultaneously lower the iron ring.
Tighten the clamp holding the glassware and tighten the iron ring. Slide a 250 mL beaker
under the U-portion of the gas delivery tube and rest it on the wire gauze, which is itself
supported by the iron ring.
Place an empty, inverted test tube over the end of the gas delivery tube (Figure 2).
Slowly fill the 250 mL beaker with water until the water level is slightly higher (~1-2 cm)
than the open end of the gas delivery tube (Figure 2a). As you are filling the beaker,
make sure to maintain the pocket of air in the inverted test tube (Figure 2b).

Dehydration of an Alcohol 86
(a)
(b)
Figure 2. Closeup view of the gas collection beaker filled with water
(a) end of gas delivery tube - water level in beaker must be higher
(b) empty inverted test tube with air pocket

This small pocket of air is critical to prevent the dreaded "suck-back" (to be discussed
later) in the initial phase of the reaction. Turn on the stir plate to mix the reagents and
turn up the heat (3:00 position). Clamp a thermometer to the ring stand and insert it into
the sand bath as close to the conical vial as possible.
While the sand bath is heating, prepare the gas collection tube. Acquire an empty
glass tube, open at both ends and insert a rubber septum into one end. Secure the rubber
septum by flipping down its upper portion over the end of the glass tube (Figure 3).
(a)

Figure 3. Gas collection tube


(a) rubber septum - sealed end
(b) (b) open end

Fill the tube completely with water. There must be no air bubble present in the tube.
Place your index finger over the open end of the tube and flip the tube upside down (the
rubber septum is now facing up at you. With your finger firmly holding the water in the
tube, lower the open end of the tube into the 250 mL beaker on the iron ring. Once the
end of the tube is below the water level in the beaker, you can release your finger and the
water should stay in the tube. If you allow a little water to fall out and air to rush into the
tube, refill the tube, and try again. This may take some practice at first, but is easy once
you get the hang of it. Let the gas collection tube sit inverted in the beaker, with open
end below the water level, while the reaction proceeds.
As the sand bath heats, the air in the vial and condenser will expand, especially
once the butanol begins to reflux. This will cause an occasional "burp" of gas from the
delivery tube, and should not be mistaken for the production of the butenes. Continue to
heat the sand bath until gas bubbles persistently and rapidly exit up from the bottom of
the empty test tube at a rate of ~1 bubble per second. In order to reach this stage of
vigorous gas production, the sand bath must usually be heated to:
~ 140 – 150 °C for 2-butanol
~ 220 – 230 °C for 1-butanol
Of course these are approximate temperatures, and you may require more or less heat,
depending on how accurately you measured the 0.30 mL of butanol.

Dehydration of an Alcohol 87
At the point of vigorous gas production, and only at the point of vigorous gas
production, remove the empty test tube from the end of the delivery tube and replace it
with the water-filled collection tube (Figure 4).

Figure 4. Placement of the gas collection tube


once vigorous gas production is observed.

Record the temperature of the sand bath at the point which you collect gas. When
moving the collection tube, be careful not to raise its open end above the water level.
Collect the gas until its production ceases, or you have completely displaced the water
from the collection tube with gas. Remove the collection tube from the end of the
delivery tube, letting it sit in the beaker, again making sure to keep its open end below
water (this traps the gas in the collection tube). Lower the iron ring and place the beaker,
with inverted gas collection tube, aside for the moment. Raise the glassware from the
sand bath and allow it to cool before you disassemble and clean it. Be careful not to
dump your spin vane or micro-stir bar into the waste container! Do not disassemble your
apparatus until you have injected your gas onto the GC and received a quality
chromatogram.
Once you remove the empty test tube from the end of the delivery tube, you
expose the open end of the gas delivery tube to water and now are at risk for "suck-back".
Any small decrease in pressure within the glassware will result in water (from the 250
mL beaker) being sucked back into the entire apparatus. As the gas is produced, pressure
in the glassware is constantly changing and your best chance of avoiding suck-back is to
not expose the delivery tube to water until you have a continuous production of gas and
continuous positive pressure. If you misjudge the rate of gas production and remove the
empty test tube too early, your risk of suck-back greatly increases. Once a small amount
of water reaches the inside of the conical vial, this cools the glassware, reducing pressure,
causing more suck-back until the entire apparatus fills with water! Despite your best
efforts, this can be difficult to avoid. You can only hope to collect enough gas (0.10 mL)
to perform the GC analysis before any suck-back occurs. If your apparatus does fill with
water before you have a chance to collect any gas, raise the entire apparatus out of the
sand bath, allow it to cool, disassemble the apparatus, clean it out and start over. There
should be enough time to repeat the reaction if necessary.

Dehydration of an Alcohol 88
Gas Chromatography Analysis of the Data
Prior to lab, your instructor will warm up the GCs using the following parameters:
• column temperature: room temp (turn to lowest setting of 24 °C)
• detector temperature: 200 °C
• injection port temperature: 200 °C
• detector current: 100
• polarity: (-)
• attenuator: 1
• He(g) flow rate: ~15 mL/min
• leave the lid of the GC oven to cool the column

For operation of the gas chromatographs, follow "Data Acquisition Procedure for Gas
Chromatographs" in Appendix A and "Data Processing Procedure for Gas
Chromatographs" in Appendix B. For the injection of your butene gas sample, use the
following specific parameters:
• inject 0.10 mL using the glass syringe in the microscale kit
• inject into Column B
• input a Run Time of 3 minutes, 30 seconds (3:30)

On the DC-200 column (column B), the order of elution follows the increasing boiling
points of the alkenes:
• 1-butene = -6.3 °C
• trans-2-butene = 0.9 °C
• cis-2-butene = 3.7 °C

Interpretation of the Data


Data from both reactions (1-butanol and 2-butanol) are needed for the
calculations, so information should be shared between you and your partner. Fill in the
flow chart/diagram below with your team's data. This flow chart/diagram is reproduced
in the Report Form. In each empty box, draw the structure for the missing
compound/intermediate. Draw the product structures and give the percent distributions
of alkenes (rounded to the nearest percent) you obtained from your alcohol and the
percent distribution from your partner's alcohol. Make sure to note your partner's name,
who analyzed the opposite alcohol, on the Report Form.

Dehydration of an Alcohol 89
2-butanol protonated
2-butanol

a % b % c %

1-butene trans-2-butene cis-2-butene

a' % b' % c' %

a**

a*

rearrangement

1-butanol protonated
1-butanol

A. Calculate the ratio of trans-2-butene to cis-2-butene formed from each alcohol.

from 1-butanol: ___________ from 2-butanol: ___________

This ratio should not depend on which butanol was reacted; it reflects the
preference of the 2-butyl carbocation to form the trans- over the cis-2-butene.
Are the ratios substantially different? Compare your trans/cis ratios to the ratio
obtained by others.

Dehydration of an Alcohol 90
B. The 1-butyl carbocation has two fates: rearrangement to form the 2-butyl carbocation
or direct elimination to form 1-butene. We can calculate the relative rates of these
different pathways (krearr/kelim) in the following way:
1. Let us assume that the 2-butyl carbocation, formed during the reaction of
1-butanol undergoes the same fate as the 2-butyl carbocation formed from
2-butanol. In particular, assume that the ratio of 1-butene to combined
2-butene products is consistent no matter which alcohol was used.
That is: a**/(b'+c') = a/(b+c).
Using your team's values obtained above, calculate the value for a** by filling the
blanks.
a b'  c'     the % 1 - butene from
a **   ________ = 2 - butyl carbocatio n
bc   from 1 - butanol

2. Now the % 1-butene formed from the 1-butyl carbocation can be


calculated by subtraction of a** from the total amount of 1-butene
observed (a′). This is the amount of 1-butene formed by direct elimination
from the 1-butyl carbocation, shown as a*.

(% a′) - (% a**) = ________ % - ________ % = ________ % a*

3. The 1-butyl carbocation either directly forms 1-butene by a* or it rearranges to


form the 2-butyl carbocation. The percent of the 1-butyl carbocation that
rearranges to form the 2-butyl carbocation can also be calculated by
subtraction:

100% - (% a*) = 100% - ________ % = ________ % rearranged

4. The relative rates of rearrangement to direct elimination is the same as the


relative percentages calculated above:

k rearr

% rearranged

   ________ =
% 1 - butylcarbo cation  2 - butyl carbocatio n
kelim %a*   % 1 - butyl carbocatio n  1 - butene

Dehydration of an Alcohol 91
C. The activation energy, Ea (Wade pg 139), is related to the rate (k) and the temperature
(T) of a reaction by
 - Ea 
 
k  Ae  R T 

where A is a constant (the frequency factor) dependant on factors such as steric


effects and concentrations, etc. For our calculations below, A will be cancelled
because we are working with relative rates of optional reactions of a single
intermediate, the 1-butyl carbocation.

We will calculate the difference in Ea for rearrangement (Earearr) and Ea for direct
elimination (Eaelim). For each rate,
 - Ea rearr   - Ea elim 
   
 R T   R T 
k rearr  Ae  
and kelim  Ae  

And the ratio of rates:


 - Ea rearr    Ea elim 
   
 R T   R T 
   
k rearr Ae e
  - Ea elim 
  rearr 
kelim     Ea 
 R T   R T 
   
Ae e

Taking the natural logarithm of both sides


 k  E elim E rearr
ln  rearr   a  a
 k elim  R  T R  T
or
k 
R  T  ln  rearr  = Eaelim - Earearr
 kelim 

If the reaction is carried out at about 120 oC (393 K)

 J  k 
 8.31   393 K   ln  rearr   Eaelim - Earearr
 mol  K   kelim 

Thus the difference in the activation energies for the two reaction paths from the
1-butyl carbocation can be calculated. Fill in the rate ratio you determined in part
B above and use the actual temperature at which the reaction was carried out:
Eaelim - Earearr =
 J 
 8.31   temp  ln rate ratio  ________ • ________• ln( ________) =
 mol  K 
__________J/mol = __________ kJ/mol

Dehydration of an Alcohol 92
CHEM 3012 - Spring 2009 Name ______________________________
Organic Chemistry Laboratory I
Partner _____________________________

Dehydration of an Alcohol – Report Form

Raw Data/Results
alcohol (1-butanol or 2-butanol): ____________________

volume of alcohol: __________ mL

sand bath temperature at gas evolution: __________ °C

Use the GC data to fill in the following table.


dehydration retention time
peak area % composition
product (minutes)
1-butene

trans -2-butene

cis -2-butene

Attach your GC chromatogram immediately after this page.

Calculations
Part A. Percent Compositions (place % composition answers in above table)

% 1-butene (show calculation):

% trans-2-butene (show calculation):

% cis-2-butene (show calculation):

Dehydration of an Alcohol – Report Form 93


Part B.
Use your data, and your partner's data (from the other alcohol) to complete the following
flow chart.

2-butanol protonated
2-butanol

a % b % c %

1-butene trans-2-butene cis-2-butene

a' % b' % c' %

a**

a*

rearrangement

1-butanol protonated
1-butanol

Part C.
Calculate the ratio of trans-2-butene to cis-2-butene (trans:cis) formed from each alcohol.

trans:cis from 1-butanol: ___________ (show calculation below)

trans:cis from 2-butanol: ___________ (show calculation below)

Dehydration of an Alcohol – Report Form 94


Part D. Activation Energy Calculations
Calculate the difference in activation energies (Eaelim - Earearr, in kJ/mol) between direct
elimination of the 1-butyl carbocation (Eaelim) and rearrangement of the 1-butyl
carbocation to the 2-butyl carbocation (Earearr). Use the actual sand bath temperature for
1-butanol in your calculation. Show each and every step of the calculation.

Part E. Energy Profile


Starting with the 1-butyl carbocation, sketch an energy profile showing the two
alternative pathways for the 1-butyl carbocation; direct elimination to 1-butene, or
rearrangement to the 2-butyl carbocation. Draw molecular structures at the typical
"reactant" and "product" positions of the profile. Label the Ea for each alternative
pathway (Eaelim and Earearr). Finally, label the Ea difference calculated above and insert
the actual kJ/mol value. Make sure the relative activation energies are properly
represented in your sketch. Make your sketch large enough to fill the remainder of the
page.

Dehydration of an Alcohol – Report Form 95


Discussion (Must be duplicated in notebook. Limit yourself to the available space.)

Conclusion (Must be duplicated in notebook. Limit yourself to the available space.)

Dehydration of an Alcohol – Report Form 96


Questions (Limit yourself to the available space.)

1. Sulfuric acid was used as the acid catalyst in this experiment.


a) Name another acid that would be practical for this reaction.

b) Why would hydrochloric acid not be a good choice?

2. Give the structures for all of the olefins produced by the dehydration of 3-methyl-3-
pentanol in H2SO4. ("Olefin" is an older term for alkene.) For each product,
begin with the given starting material and write the complete, detailed, step-by-
step mechanism leading to its formation. Make sure to show the flow of electrons
by using curved arrows, as well as all charges and lone pairs where appropriate.
Show all steps. Do not take shortcuts. Lastly, circle and label the expected major
product.

Dehydration of an Alcohol – Report Form 97