Green Chemistry – Need and Goal

Definition

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 Risk = f(Hazard, Exposure)

The traditional i.e. old way of reducing

risk → by reducing exposure
Through protective equipment, safety devices
and other control methods
(However controlling exposure does not
remove inherent threat of hazard!)

Green Chemistry Approach: Remove the use of hazardous substance in all levels
– from starting materials, auxiliary chemicals or solvents, intermediate species,
catalysts (if used) unto the end product.
A variety of techniques and methodologies will be required!!
However, this hazard-reducing protocol, when applied properly, will bring down risk to ZERO.
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 Green Chemistry – Sustainability Goals

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• Manufacturing processes have to try to generate as little waste as possible, through
reaction choice, process design and recycling.

• Industry should aim to use chemical reactions and processes that make the most
effective use of available resources and generate the smallest possible amount of
waste material.

In this regard, a guiding factor can be the YIELD of a chemical reaction:

the efficiency of a chemical process is indicated by the yield, which compares the
expected product quantity with the actual amount obtained.

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 𝑀𝑎𝑠𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
𝑌𝐼𝐸𝐿𝐷 % = × 100 %
𝑀𝑎𝑠𝑠 𝑒𝑥𝑝𝑒𝑐𝑡𝑒𝑑 𝑓𝑟𝑜𝑚 𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑦

An example is the manufacture of phenol

(phenol)
• The chemical equation shows that 1 mole of benzene (78 g) should yield 1 mole of
phenol (94 g).
• In practice, the quantity of phenol produced is found to be about 77 g, giving a yield
of 82%. (This is a reasonably good yield!)
• However, the calculation obscures the fact that the reaction also generates 1 mole
(126 g) of sodium sulfite for each mole of phenol produced!
• This unwanted product may present a serious problem of waste management and
adds significantly to costs.
Bottom line : the yield of chemical reaction is not sole benchmarking criterion.
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• It is an alternative measure to yield, and one of the key ideas behind the concepts of
green chemistry.
• Atom Economy expresses the proportion of reactant atoms that end up in a useful
product, measuring the number of atoms of the starting materials that end up as
desired product(s).

Atom economy is defined as

Atom 𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

% = × 100 %
Economy 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠𝑒𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑎𝑛𝑡𝑠

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 Atom 𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
% = × 100 %
Economy 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠𝑒𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑎𝑛𝑡𝑠

Q. Calculate the Atom Economy (%) for the following two reactions and predict which one
will be more Green in terms of atom economy principle:

1.
Desired product Ans. 42%

2.
Desired product Ans. 87%
Here, Ph = C6H5, Cr = 52, S = 32.

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Let us go back to the manufacture of phenol:

Calculate the atom economy for this reaction. Ans. 37%

This poor atom economy actually now accounts for the unwanted and undesired product!
Because, it has to be noted that,
Atom 𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
% = × 100%
Economy 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠𝑒𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑎𝑛𝑡𝑠
𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
= × 100%
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠𝑒𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑓𝑜𝑟𝑚𝑒𝑑

• Some reactions that have 100% atom economy have poor yields and so it is necessary
to consider both measures of efficiency, yield and atom economy.
• Atom economy is determined in the planning stage, by calculation, while yield can only
be found experimentally.
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• This invokes the fundamental principle of green chemistry that aim to minimize or eliminate hazard in all
aspects of the design of chemistry.
• Risk or harm (to health or environment can be minimized by reducing the hazard or by minimizing the
exposure.
• The “exposure control” will always have an additional cost burden because of requirement of many
engineering controls and protective gears etc. Also there is always the threat of potential failure of exposure
control mechanism – environmental disaster!
• On the other hand, chemists have the knowledge and skills to minimize the hazard faced by public, the
environment, and the user of chemicals in general.
• So, unlike the old school method of protecting the environment and through limitation, regulation, or
elimination of chemicals or chemistry, the GREEN CHEMISTRY approach actually embraces chemistry as a
solution rather than a problem.
• Thus, designing and developing processes that eliminates the hazard of a synthetic maneuver is the solution
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chemistry, chemical laboratories and industries. 9
• The aim is to produce chemicals that are useful yet both safe for humanity and environment.
• Because of the structure-property relationship, knowledge of chemical structure can be used
to characterize the toxicity of molecules.

Examples:
Safer polymers: Developed to be much less flammable than the more well known polymers but also
retain properties such as toughness. They must be able to absorb severe impacts without cracking
and breaking. Example is polyphenylsulfone:

Used in interior panels of aircraft

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 Easily degradable detergents: Washing detergents end up in water courses or in
household waste for landfill. In both these cases, the material should degrade to
harmless products.
• Normally these detergents are based on the sodium salts of alkylbenzene sulfonic
acids, and the alkyl group are branched. These are not degraded naturally.
• Now these compounds are being replaced with sodium salts of linear alkylbenzene
sulfonic acids, which are readily degraded.

Basic approaches for designing safer chemicals industrial chemical processes:

1. Preventing the reactions through which the toxic mechanism is carried out.
2. If exact mechanism is not known then identify the functionality (or the functional groups)
that has the relation to toxicity, and eliminate that functionality to prevent toxic effect.
3. Minimize the bioavailability: If a certain substance is toxic and yet it cannot reach or
accumulate in the target organ (e.g. lungs, liver, stomach) then it is rendered ineffective for
practical purposes.
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• Use of Volatile Organic Compounds (VOCs) as solvents and separating media in industrial scale
productions has led to major environmental concerns as these compounds are pollutants as well as
toxic.
• These VOCs can be replaced by a number of benign alternatives, such as,
(a) Supercritical fluids: Like supercritical carbon dioxide (CO2) whose liquid property can be tuned by
changing temperature and pressure. Since CO2 is non-toxic gas, its use in the liquid form will not be
harmful.
(b)Water as a solvent: Water is the only solvent which is ABSOLUTELY harmless. So Green Chemistry
promotes chemical reactions in water. (Development of water-borne paints, which can replace
normal paints that use volatile hydrocarbons as solvents is an illustrative example)
(c) Solvent-free methods: In chemical reactions often a reactant can act as a solvent; designing these
processes will obviously reduce the auxiliary substance (solvent)
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Minimization of energy consumption is key attain long-term environmental benefit and
sustainability, because
1. Energy sector overwhelmingly dependent on fossil fuel (Petroleum, coal, natural gas) and the
resources are depleting,
2. Fossil fuel burning is major source environmental pollution.
Thus green technology obviates the need for energy saving approach.

General chemical reaction:

1. Common practice is to heat the reaction mixture to reflux condition – for activation
purposes.
2. Also, for quenching the reaction or controlling reaction rate or crystallization of
products – cooling is invariably use.
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Green chemistry approach:
• To optimize a reaction or the entire synthetic pathway to minimize the energy
demand - to carry out the reactions at ambient temperature and pressure.
• Catalysis – Catalysts bring down the reaction activation energy and so the
temperature of the reaction.
• To reduce, if possible, the energy-consuming separation/purification methods like
distillation, recrystallization (by cooling) etc.
• Use alternate energy sources like Microwave (rapid heating – so more efficient),
ultrasound (less energy demanding) etc.
• And also minimizing other modes of energy loss
 Maintenance – Good insulation and well-maintained equipment will reduce heat
loss, save energy.
 Combined heat and power (CHP) – If manufacturing sites generate their own
electricity rather than buying from the grid, then it eliminates transmission losses,
and the excess heat released during production can be used on site for other
purposes.
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• Fossil fuel based chemicals – obtained during petroleum refining or naphtha cracking: Depleting
feedstock.
• Biological feedstock is generally considered renewable feedstock.
• CO2 is renewable feedstock.

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• A catalyst is essentially an agent that will change the rate of a chemical reaction without being
changed in the process.
• Because of that a catalyst is typically required in minute amount compared to the stoichiometry of
the reactants and products.

From Green Chemistry perspective catalysis is superior because,

• Selectivity: Often the catalysts are very selective in controlling one or of the following factors
(a) The degree of reaction
(b) The site of reaction
(c) The stereochemistry of reaction etc.
This improves atom economy and minimize unwanted byproducts (waste).
• Energy Minimization: Catalysts provide alternate reaction pathway by lowering the activation energy
of the reaction, thereby reducing temperature of the reaction as well as shortening the reaction time.
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Catalysis: An Example
Synthesis of LAZABEMIDE, an anti-Parkinsonian drug, which was originally synthesized in eight
steps starting from 2-methyl-5-ethylpyridine, is possible in one step by Palladium catalyzed C–C
bond formation reaction with 65% yield and 100% atom efficiency.

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Materials that are not degraded naturally or does not undergo biodegradation are major
issue for environment, e.g.,
• Plastics – causes serious environmental pollution and threaten various life-forms
• Pesticides – tend to accumulate in animal tissues, major toxicity issue.

Green Chemistry solution: In designing new material as we look up for various functions,
one has to consider degradation also as a function of that material.
Example:
• pyrethoid pesticides which have the duel benefits of breaking down in sunlight in 2-3
days and have much lower acute toxicity to humans than phosphorus, or chlorine-based
pesticides.
• Biodegradable plastics - has been made with limited lifetime.
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 Examples
(a) Adipic Acid Manufacturing:
Adipic acid is a very commercially valuable chemical with world production of ~2 million ton year-1,
the majority of which goes into the manufacture of Nylon 6,6.
Conventional route to Adipic acid manufacturing:
Two stage process – (a) From benzene to the mixture of cyclohexanol + cyclohexanone, (b) nitric acid
treatment of this mixture to adipic acid.

(from Petroleum)

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 Examples
(a) Adipic Acid Manufacturing: Conventional Route

A number of green and sustainability issues

Carcinogenic; also, from petroleum Energy demanding (high
feedstock (non-renewable) temp. & pressure)

overall poor atom

economy

(from Petroleum)

Hazardous nitric
A greenhouse
acid oxdn
gas!
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(b) Catechol Synthesis:
This chemical is used in synthesis of a number of commercial products like pharmaceuticals,
agrochemicals, antioxidants etc.
Conventional route to Catechol synthesis:
A multistep reaction starting with benzene, and ultimately leading to a mixture of two alcohols.

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(b) Catechol Synthesis: Conventional Route

The conventional route suffers from several limitations

Carcinogenic; also, from petroleum Phenol is a toxic
feedstock (non-renewable) intermediate

overall poor atom H2O2 is highly

economy corrosive

Large amount of byproduct,

so further separation needed;
Also byproduct creates excess
environmental burden

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Green Synthesis of Catechol and Adipic Acid: From Glucose to adipic acid via
catechol – using biocatalysis by genetically modified E. Coli bacteria

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 Exercise 1.
In the context of Green Chemistry Principles, which reaction is more preferable ? Explain
by invoking the relevant Green Chemistry Principles.

COOH
H
N N
Catalysts
+
Room temp.
4-10 min

(A)

COOH ZnCl2 above

H stoichtometrica
N N
amount
+
200-2700C
20 hrs
(B)

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Exercise 2.

(a) Calculate the atom economy for the desired product of the two reactions, and
state which one is more green.
(b) From 1 kg of starting material A, the yield of B in the 1st reaction is 50% and in the
2nd one is 90%. Calculate the amount of B in kg for both reaction. Which one is
more green from yield perspective?
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