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ACS Chemistry Laboratory Supplement

Project-Based Labs

Green Oxidation
Introduction
Your company, Acme Oxidation, has been cited and fined by the Environmental Protection
Agency (EPA) for being in non-compliance with regulations concerning the release of
chromium(VI) oxide, a known toxic substance, into the sewer system. To save your company,
you must find a green chemistry approach to your business of oxidizing alcohols. In the past,
oxidation of alcohols has been performed using chromium or some other heavy metal in a high
oxidation state. You have been notified that, in the future, you must either use some more
environmentally benign oxidizing agent, or possibly find a way to recycle the metallic oxidizing
agent.
Preliminary research has given rise to some promising leads. It is your job to figure out
which alternative oxidation method is the most effective, environmentally friendly, and
economically viable.
For your initial trials, you will use
OH
benzhydrol as your starting alcohol. This is its
C
structure. For additional information about
H
alcohols, see the resource section that follows.
The oxidants available to you are Clorox
household bleach, which contains sodium hypochlorite, and a material called Magtrieve, which
contain CrO2. Magtrieve is used on the surface of audiocassette tapes. The bleach you can use
as is and you will be supplied with Magtrieve as a powder.

Project Tasks
Some of these tasks will be accomplished experimentally and some by library or web-based
research in appropriate resources.
1. Investigate each oxidizing agent to find which works best for benzhydrol oxidation.
2. Identify the byproducts that remain after reactions of the oxidants.
3. Decide which of these oxidants is the most environmentally friendly.
4. Consider which oxidant will be the most cost effective for Acme Oxidations.
5. Determine if either oxidant is recyclable.
6. Determine if results observed with benzhydrol can be reproduced with other alcohols.
7. Optional: Use thin-layer chromatography to follow the course of the reaction.
8. Optional: Use infrared (IR) analysis to determine if the alcohol has been oxidized.

Learning and Performance Objectives


1. Perform the oxidation of an alcohol by two different methods.
2. Purify and identify the oxidation product.
3. Find the melting point of the reactant alcohol and the product that forms.
4. Oxidize more than one alcohol by each method.
5. Handle flammable liquids safely.
6. Use your chemical knowledge to solve real world problems.

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Project-Based Labs

ACS Chemistry Laboratory Supplement

Resources Available
1.
2.
2.
3.
4.

A brief discussion of alcohols


A strategy for oxidizing alcohols using Clorox
A strategy for oxidizing alcohols using Magrieve
A method for measuring melting point
Suggestions for other analytical tools that can be useful in this project

Reports
1. Planning sheets are to be completed as directed by your instructor.
2. The final report for this project should follow the basic guidelines given previously.
Be sure to include:
a. observations and other results from all group experiments.
b. references for all information from the web or other resources
c. comparison and contrast of the two possible oxidation methods, and their
advantages over the original method.
3. Be sure you support your report recommendations with data from the various aspects of
the project, including cost, safety, environmental impact, and effectiveness in oxidizing
the alcohol.

Materials Available: Chemicals and Equipment


Clorox (household bleach), Magrieve powder, acetic acid, benzhydrol, benzophenone, ether,
acetone, toluene, ethyl acetate
Optional: Thin-layer chromatography (TLC) plates, toluene/ethyl acetate developer
Infrared spectrometers
Melting point apparatus
Safety Information
You should assume that all organic solvents are flammable. They should be handled in a
hood. There should be no open flames in the lab during this project. Instead, use a hot plate with
a water bath or a sand bath to heat samples.
All mixtures containing chromium ion must be placed in appropriate containers for later safe
disposal. Chromium compounds are toxic and pose danger to the environment. Do not allow
chromium, particularly in high oxidation states, to go down the drain.

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Project-Based Labs

Techniques You May Need


Glassware setup for heating a reaction
Refluxing
Extraction
Product isolation by salting out
Recrystallization
Recycling processes
Waste disposal
Optional: Thin layer chromatography (TLC)
Optional: Infrared chromatography (IR)

Resource: Alcohols
All alcohols contain a covalently bonded OH group. They are commonly classified
according to their structures into three types; primary, secondary, and tertiary alcohols.
Primary Alcohol

Secondary Alcohol

Tertiary Alcohol

H
R C OH
H

H
R C OH
R'

R''
R C OH
R'

Primary alcohols are generall oxidized to aldehydes under the conditions of this project; they
may be oxidized all the way to carboxylic acids by stronger conditions. Secondary alcohols are
typically oxidized to ketones. Tertiary alcohols cannot be oxidized under the conditions in this
project. There must be at least one hydrogen on the carbon containing the OH group for the
oxidation to be effective using either Clorox or Magtrieve.
Resource: Oxidation Using Clorox
This equation shows the general process for the oxidation of a secondary alcohol using
sodium hypochlorite.
R2CHOH + NaOCl R2CO + NaCl + H2O
To carry out this oxidation, start with 1 gram of alsohol and dissolve it in 1 M acetic acid.
From the stated concentration on the label, calculate how much bleach you will need to oxidize
the alcohol sample. Add bleach drop by drop over a 45-minute period.
Use some of the product and use TLC to check whether or not the reaction has taken place.
When all of the alcohol appears to have reacted, or after 2 hours, add ice water to dilute the
reaction mixture. Make the acetic acid more water soluble by adding solid sodium carbonate or
sodium bicarbonate until there is no additional effervescence.
See if your product crystallizes. If so, filter, dry and recrystallize the product. If your product
will not crystallize, extract the product with three portions of ether, dry the ether extracts, filter
and evaporate the solvent with a gentle stream of air of nitrogen gas. Then recrystallize the
product.
Characterize the isolated product as indicated by your instructor.

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ACS Chemistry Laboratory Supplement

Resource: Oxidation Using Magtrieve


This equation shows the general process for the oxidation of a secondary alcohol using
Magtrieve.
R2CHOH + CrO2 R2CO + Cr2O3
To carry out this oxidation, start with 1 gram of alsohol and dissolve it in dichloromethane.
Add about 100 mg of Magtrieve and reflux for 2 hours. Stop the reflux and allow the mixture to
cool to room temperature.
Use some of the product and use TLC to check whether or not the reaction has taken place.
When all of the alcohol appears to have reacted, hold a magnet to the bottom of the reaction
flask, decant supernatant liquid onto calcium chloride solid. Filter the liquid to remove the
calcium chloride, and evaporate the dichloromethane.
Purify the product by simple distillation if it is a liquid. If it is a solid, use recrystallization
procedures as before. Characterize the product in the usual manner.
Heat Magtrieve in an oven at 250C overnight to recycle the catalyst. The same sample can
now be used to repeat the oxidation procedure with another sample of alcohol.

Resource: Other Useful Analytical Methods


If thin-layer chromatography (TLC) methods are to be used to track the progress of the
reaction, your teacher will give you more experimental details. It is necessary to combine a small
sample of alcohol with Clorox in a test tube. This mixture can be used to spot the TLC plate,
along with parallel samples of the reaction mixture over time. The combination of alcohol and
Magtrieve can be directly spotted on the plate.
Another useful tool is infrared (IR) spectroscopy. Again, your teacher will provide more
experimental details if appropriate equipment is available. This analytical tool provides a quick
method of determining if the alcohol has been oxidized to an aldehyde, ketone, or carboxylic
acid.

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Project-Based Labs

Green Oxidations: Planning Sheet 1


Group Name
To be completed before starting experimentation.
State the overall purposes of this project in your own words.

1. Look on the web or in another source to find a definition of green chemistry. Rephrase the
definition in your own words.

2.

What are the advantages of green chemistry procedures?

3. What is the chemical formula for benzhydrol? What type of alcohol is benzhydrol? What are
its properties? Report any references used to help answer these questions.

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4.

ACS Chemistry Laboratory Supplement

Which functional group is changed by the procedures that you will carry out in lab? Draw
out each reaction scheme using structural formulas for each procedure. Identify the new
functional group produced by the oxidation.

5. If fresh household Clorox is 5.25% by weight NaOCl, what volume of bleach should you use
to oxidize 1 g of alcohol? Show your work.

6. Exactly which species in bleach is the oxidizing agent? How do you know?

7. What is the oxidation number of chromium in Magtrieve? How do you know?

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Green Oxidations: Reflection and Planning Sheet 2
To be completed after the first laboratory period.

Project-Based Labs
Group Name___________________

State the purposes of this weeks lab in your own words.

1. Describe how you obtained and identified your product from the bleach oxidation.

2. Describe how you obtained and identified your product from the Magtrieve oxidation.

3. Compare the two methods for ease of use, purity of product, and percentage recovery.

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4. What property of Magtrieve makes its separation from your reaction mixture quick and easy?

5. Magtrieve was recycled by heating it in an oven at 250 C. What do you think happens to the
Magtrieve during this process? Explain your reasoning.

6. What additional information will be needed before next week, when your boss at Acme
Oxidation wants a draft of your report presented at the Board of Directors meeting?

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Green Oxidation: Reflection and Planning Sheet 3
To be completed after the second laboratory period.

Project-Based Labs
Group Name___________________

State the purposes of this weeks lab in your own words.

1. Describe the results of any additional experimentation that your group carried out today in
lab.

2. Which method of oxidation is the greenest? Define your terms and decide how you will
communicate this information to your boss.

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ACS Chemistry Laboratory Supplement

3. Which method of oxidation is the most economical? Give references used to gather this
information.

4. What additional points will you include in your final report to the boss? How will you
organize your report? Communicate the criteria by which you are judging the best
oxidizing agent for this company to use. Outline your groups ideas.

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Green Oxidation