UNS

Sebelas Maret
University

GREEN CHEMISTRY

By:
Dr.rer. nat. Maulidan Firdaus,
M.Sc.

GREEN CHEMISTRY, AN INTRODUCTION

Green Chemistry,
Sustainable Chemistry,
Clean Chemistry,
Environmentally Benign Chemistry

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Sebelas Maret
University

GREEN CHEMISTRY, AN INTRODUCTION

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Sebelas Maret
University

CHEMISTRY - PAST, PRESENT, AND FUTURE

An exaggerated but illustrative view of twentieth century chemical
manufacturing can be written as a recipe :

1.
2.
3.
4.
5.

Start with a petroleum-based feedstock.

Dissolve it in a solvent.
Add a reagent.
React to form an intermediate chemical.
Repeat (2)(4) several times until the final product is obtained;
discard all waste and spent reagent; recycle solvent.
6. Transport the product worldwide, often for long-term storage.
7. Release the product into the ecosystem without proper evaluation of its long-term effects, ex: DDT.

DDT
DDT

Grashopper Effect
Bioaccumulation

DDT

DDT

win
d

DDT

Biomagnification
Biodegradation

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Source: Majewski et al, 1995

ACID RAIN ???

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Major sources of pollution: Industrial furnaces: SO 2, NOx

WHAT IS THE EFFECT OF THE INPUT OF ACIDITY ON THE SOIL:

This depends on the soil minerals, the input quantity, and time. First
the forests react with more growth! Nitrogen and sulfur are
macronutrients! Eventually, however, the soil chemistry changes
dramatically.
The problem which arises now is the Aluminum from the silicate
weathering. At an pH of ~ 5, the Al from the minerals is converted
to aluminum hydroxide Al(OH)3. This compound can enter the root
cytoplasm, forming complexes and interfere with the cell
metabolism like heavy metals.
If, however, the acid input continues further, then the following
reaction takes place: Al (OH)3 + 3 H+
Al3+ + 3 H2O
This takes place at an pH of about 4.2 Al3+ binds to the carboxyl
groups of the pectin of the cell walls of the root cortex of the forest

CHEMISTRY - PAST, PRESENT, AND FUTURE

The recipe for the

twenty-first

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century will be very different:

1. Design the molecule to have minimal impact on the environment

(short

residence time, biodegradable).

2. Manufacture from a renewable feedstock (e.g. plant oils,

carbohydrate, etc)
3. Use a long-life catalyst.
4. Use no solvent or a totally recyclable benign solvent.
5. Use the smallest possible number of steps in the synthesis.
6. Manufacture the product as required and as close as possible to
where it is required.

Reduction of p-Anisaldehyde (3)

to 4-Methoxybenzyl alcohol (4)
H

4 H

3
H

O BH3HO

OH

O
OCH3

H2C

H
H

+ (OH)4B

H
OCH3

(3)

OCH3

OCH3

(4)

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Sebelas Maret
University

Bromination of 4-Methoxybenzyl alcohol (4)

+
H2C

Br

OH

Br

P
Br

Br
Br
Br
HO

Br
P
Br

OCH3

OCH3

(4) 4-methoxybenzyl bromide

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Comparison of Synthetic Procedure for the

Transformation of p-Anisaldehyde
to 4-methoxybenzyl bromide

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Procedure
Reaction

Reduction of
p-anisaldehyde

Green Methodology

Solution Phase Methodology

- Solvent-free
- Large volume of solvent (~ 50
- Grinding at room temperature mL ethanol)
- Complete in 10 minutes
- reflux at 80C for 3 hours
- Yield 98% (Firdaus, 2008)
- Yield 55% (Sardjono, 1999)

- Solvent-free
- Large volume of solvent (~ 40
Bromination of - Stirring at -5C for 1 h to be
mL dichloromethane)
4-methoxybenzyl followed at room temperature - reflux at 40C for 4 hours
alcohol
for 2 h
- Yield 83% (Hadanu, 2008)
- Yield 86% (Firdaus, 2008)

GREEN
CHEMISTRY

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Sebelas Maret
University

DEFINITION
Green chemistry is a form of pollution prevention. It is
most simply defined as the use of chemistry techniques
and methodologies that reduce or eliminate the use or
generation of feedstocks, products, byproducts, solvents,
reagents, etc. that are hazardous to human health or the
environment
GREEN CHEMISTRY IS ABOUT

Waste Minimization at Source

Use of Catalysts in place of Reagents
Using Non-Toxic Reagents
Use of Renewable Resources
Improved Atom Efficiency
Use of Solvent Free or Recyclable Environmentally Benign

Green Chemistry Is
About...
Waste
Materials
Hazard

Reducing

Risk

Energy
Environmental Impact

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COST

Pollution Prevention Hierarchy

Prevention & Reduction

Increasing Greenness

Recycling & Reuse

Treatment

Disposal

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THE ECONOMICS OF GREEN CHEMISTRY

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University

From an economic standpoint, the green chemistry approach has many

advantages. The costs associated with regulatory compliance including
factors such as waste treatment, disposal costs, and waste control.
Environmental compliance budgets of individual chemical companies
rival those funds chosen for research and development. On the

often

other hand,

implementation of green procedures could potentially suc- ceed in lowering

feedstock costs, increasing conversion rates,

decreasing reaction

times, improving selectivity, enhancing separations, and lowering the energy

required for reactions. As a result, industry

could experience significant

financial gain if green methods were to be successfully adopted.

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APPLICATIONS IN ACADEMIA

Sebelas Maret
University

Although the major portion of chemical waste produced comes from

industry, significant amounts of hazardous materials are released into the
environment by academic laboratories. Out of date procedures employing
traditional and hazardous reagents are common, especially in
undergraduate laboratories. While the adoption of microscale techniques
has substantially improved the environmental position of academic
laboratories, a considerable problem still remains. Disposal costs often
comprise a large portion of a departments budget. In addition to the
financial drain placed on the chemistry department, the use and produc- tion of
hazardous waste pose a constant danger for the student. Little
progress,
however, has been made in transforming the academic labora-tory into a space
that is environmentally sound.