Green Chemistry

The Green Chemistry Assistant:

Expanding the horizons of green
chemistry in chemical education
Robert M. Hanson, Paul R. Campbell,
Elizabeth R. Johnson, Gary O. Spessard,
and Marc A. Klingshirn

St. Olaf College

Northfield, MN 55057
hansonr@stolaf.edu
231st ACS National Meeting, Atlanta, Georgia
March 27, 2006
Green Chemistry

My Goals Today

Briefly discuss the important

distinction between equations and
reactions, and between reactions
and processes.

Introduce a new web-based tool

the Green Chemistry Assistant.
Green Chemistry

My Goals Today

Share what we have learned about

our students from using the GCA.

Share what we have learned about

green chemistry from our students.
Green Chemistry

Three Levels of Green Chemistry

Equations

HCl (aq) + NaOH (aq) NaCl (aq) + H2O (l)

Green Chemistry

Three Levels of Green Chemistry

Reactions

http://www.uncw.edu/smec/gk_fellows/askscience.html
Green Chemistry

Three Levels of Green Chemistry

Processes

www.shelldeerpark.com/chemical.htm
Green Chemistry

Three Levels of Green Chemistry

Equation

Atom Economy = 40%

Green Chemistry

Three Levels of Green Chemistry

Reaction

Atom Economy = 40%

Green Chemistry

Three Levels of Green Chemistry

Reaction
Green Chemistry

Three Levels of Green Chemistry

Reaction
Green Chemistry

Three Levels of Green Chemistry

Reaction
Green Chemistry

Three Levels of Green Chemistry

Reaction

Atom Economy = 40%

Green Chemistry

Three Levels of Green Chemistry

Reaction

Atom Economy = 40%

before after
Green Chemistry

Three Levels of Green Chemistry

Reaction Excess, Limiting Reactant

Experimental
Atom Economy = 26%

before after
Green Chemistry

Three Levels of Green Chemistry

Process...

unrecyclable
silica gel
unrecovered
CH2Cl2 Process Mass
Efficiency = 1%

provides context
Green Chemistry

Three Levels of Green Chemistry

Process

Process Mass
Efficiency = 10%

can involve more than one step

Green Chemistry

Three Levels of Green Chemistry

Process
Process Mass Process Mass
Efficiency = 1% Efficiency = 10%

allows for comparison

Green Chemistry

Three Levels of Green Chemistry

Equation, Reaction, and Process

Wouldnt it be nice to have access to a

tool that would allow us to quickly
make comparisons like this?
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca

Based on the EPA Green

Chemistry Expert System

User-friendly interface
designed to assist students
in analyzing the atom
economy, and safety of
chemical processes
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

My Goals Today

Share what we have learned about

our students from using the GCA.
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca

Lessons learned:
Students need help just writing the
balanced chemical equations.
Process is important, as most real
experiments involve more than one
process step.
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca

Lessons learned:
We need lab manuals that are more
explicit in guiding students to an
understanding of the overall set of process
steps they will be carrying out.
Green Chemistry

My Goals Today

Share what we have learned about

our students from using the GCA.

Share what we have learned about

green chemistry from our students.
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca

Lessons learned:
Introducing green chemistry provides a
rich context for discussing safety,
including nomenclature, CAS registry
numbers, MSDS sheets, and health and
environmental hazards.
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca

Lessons learned:
All is not as simple as one might think
from what is in the literature in terms of
the definitions of green measures.
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca

TsCl / Et3N
OH OTs

Question:

What is the balanced chemical equation for this

reaction?
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca

OH + TsCl

OTs
+ HCl

Is it this?... (atom economy = 88%)

Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca

OH + TsCl + Et3N

OTs
+ Et3NHCl

or this? (atom economy = 66%)

Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
On assumptions regarding atom economy:
The process of calculating atom economy may be
simplified by only considering key reactants. For example,
catalysts used in stoichiometric quantities, or the acid or
base used in hydrolysis, are considered to be reactants. These
examples are in contrast to common inorganic reagents, even
when used in stoichiometric quantities (e.g. potassium
carbonate), which have been ignored. Inorganic reagents
and/or other material are not included in the calculations as
long as at least two other reacting substances are identified.

Constable, Curzons, and Cunningham, Green Chemistry, 2002, 521-527

Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca

1) BH3 THF
OH
2) H2O2/NaOH

Question:

What is the balanced chemical equation for this

reaction?
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca

1) BH3 THF
OH
2) H2O2/NaOH

Question:

Is this one reaction or two?

Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca

1) BH3 THF
OH
2) H2O2/NaOH

Question:

What is the atom economy?

Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
STEP
1
3 + BH3THF B
+ THF
3
STEP
2 B + 3 H2O2 3 OH + NaB(OH)4
+ NaOH
3

Overall Atom Economy = 60%

Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
STEP
1
3 + BH3 B
3
STEP
2 B + 3 H2O2 3 OH + NaB(OH)4
+ NaOH
3

Overall Atom Economy = 72%

Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
STEP
1
3 + BH3THF B
+ THF
3
STEP
2 B + 3 H2O2 3 OH + NaB(OH)4
+ NaOH
3

STEP
3 BH3THF + 3 H2O + NaOH THF + NaB(OH)4 + 3 H2 (g)

In practice, Step 3 is important!

Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca

Lessons learned:
Getting students thinking about the overall
process is good.
Expecting them to do it on their own because its
simple is asking too much.
The Green Chemistry Assistant enables us to
explore the nature of green chemistry processes
and green chemistry measures.
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Faculty
Gary Spessard, Marc Klingshirn, Paul Jackson
Students
Paul Campbell, Allison Christensen, Elizabeth R.
Johnson, Tim Barker, Tyler Drake, David Harris
Technology Support
Dan Beach
Financial support
WM Keck Foundation
Howard Hughes Medical Institute
Green Chemistry

Green Chemistry Assistant

http://fusion.stolaf.edu/gca
Upcoming double-header symposia of possible
interest in 2006:

Web-Based Applications for Chemical Education

ACS CCCE online CONFCHEM, May 5 June 30
www.stolaf.edu/depts/chemistry/bh/confchem

Web-Based Applications for Chemical Education

19th BCCE, July 31 Aug 2