Chemistry

of the
Environment
 Syllabus

Goals of green chemistry – Limitations

Twelve principles of green chemistry with their explanations

and examples

Prevention of waste / byproducts

Atom economy (maximum incorporation of materials used in

the process)

Minimization of hazardous / toxic products

Prevention of chemical accidents

Chemistry
of the

Green synthesis – Designing a green synthesis Environment
• Hazardous = Dangerous

• Benign = Caring, Kindly, Generally

• Paradigm = Pattern

• Spur = Encourage

• Ingenuity = Cleverness

• Innocuous = Harmless, safe

• Efficacy = Efficiency Chemistry

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 Chemistry
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 What is Green Chemistry?

Green chemistry is the sustainable practice of

chemical science and manufacturing within a
framework of industrial ecology in a manner that is
sustainable, safe, and non-polluting, consuming
minimum amounts of energy and material
resources while producing virtually no wastes

Chemistry
of the
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 Chemistry
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 The invention, design and application of chemical
products and processes to reduce or to eliminate the use and
generation of substances hazardous to human health and the
environment

Fundamental and innovative chemical methods that

accomplish pollution prevention through source reduction
“The use of chemistry for source reduction”

“Sustainable chemistry” is the design, manufacture and

use of efficient, effective, safe and more environmentally benign
chemical products and process
Chemistry
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 Green Chemistry is Sustainable
• Economic: At a high level of sophistication, green
chemistry normally costs less in conventional economic
terms (as well as environmental costs) than chemistry as it
is traditionally practiced

• Materials: By efficiently using materials, maximum

recycling, and minimum use of virgin raw materials,
green chemistry is sustainable with respect to materials

• Waste: By reducing in so far as possible, or even totally

eliminating their production, green chemistry is sustainable
Chemistry
with respect to wastes of the
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Green Chemistry represents a major model that focuses on
environmental protection at the design stage of product and
manufacturing process

It is an innovative way to deal with chemicals before they

become hazards, with the goal of making chemicals and
products “Benign by Design”

Chemistry is an opportunity to encourage the next industrial

revolution through human cleverness and creativity

Advancing Green Chemistry is an opportunity to make a

safer and more efficient world with less waste
Chemistry
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• Reduced exposure: The hazard remains, but exposure to
it is reduced, such as by wearing safety goggles around
an eye hazard

• Reduced hazard: The hazard is diminished or eliminated

at its source; measures still may be taken to reduce
Chemistry
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exposure to remaining hazard
 Chemistry
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 Chemistry
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 Chemistry
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 Chemistry
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The Twelve Principles of
Green Chemistry

Chemistry
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 Prevention

It is better to prevent waste than to treat or

clean up waste after it is formed

Chemistry
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 Chemistry
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 Classic Route to Ibuprofen
HCl, AcOH, Al W aste HCl AcOH

Ac 2 O H 2 O / H+
ClCH 2 CO 2 Et
AlCl 3
NaOEt

COCH 3

EtO 2 C
O OHC

NH 2 OH

H 2 O / H+

N OHN
HO 2 C
Chemistry
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NH 3
Hoechst Route To Ibuprofen

AcOH

HF H2 / Ni CO, Pd
Ac2O

O HO HO2C

Chemistry
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 Atom Economy

Synthetic methods should be designed to

maximize the incorporation of all materials used in
the process into the final product

Chemistry
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 Chemistry
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 Chemistry
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• Calculate the percentage atom economy in the formation of
1-iodiopropane from 1-propanol according to the following
reaction
CH3CH2CH3OH + NaI + H2SO4  CH2CH2CH2I + NaHSO4 + H2O
Formula of Molar Mass Atoms used in Sum of Molar Unused Sum of Molar
Reactants of Reactants Product Mass of Used Atoms Mass of
Atoms Unused
Atoms
CH3CH2CH2OH 60.1 3C, 7H 43.1 HO 17.0
NaI 149.9 I 126.9 Na 23.0
H2SO4 98.0 - 0 2H, S, 4O 98.0
Total Atoms in 308.0 3C, 7H, I 170.0 HO, Na, 2H, S, 138.0
Reactants, 3C, 4O
10H, 5O, Na,
S, I

Percentage Atom Economy =

Chemistry
(molar mass used atoms / molar mass of all reactants) x 100of the
Environment
= (170.0/308.0) x 100 = 55.2%
 Chemistry
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 Atom Economy
Balanced chemical reaction of the epoxidation of styrene
O
O O O OH
OH

+ +

Cl Cl

Assume 100% yield

100% of the desired epoxide product is recovered
100% formation of the co-product: m-chlorobenzoic acid
A.E. of this reaction is 23% Chemistry
of the
77% of the products are waste Environment
• If the chemical reaction of the type

• A+B P+W

• Find alternate A or B to avoid W

• Example 1:

• Disinfection of water by chlorination. Chlorine oxidizes the

pathogens there by killing them, but at the same time forms
harmful chlorinated compounds.

• A remedy is to use another oxidant, such as

O3 or supercritical water
oxidation Chemistry
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 Example 2 of green chemistry
• Production of allyl alcohol CH2=CHCH2OH

• Traditional route: Alkaline hydrolysis of allyl chloride, which generates the

product and hydrochloric acid as a by-product
C H 2= C H C H 2C l + H 2O C H 2= C H C H 2O H + H C l

p ro b le m p ro d u c t

• Greener route, to avoid chlorine: Two-step using propylene (CH2=CHCH3), acetic

acid (CH3COOH) and oxygen (O2)
CH 2=CHCH 3 + CH 3 COOH + 1/2 O 2 CH 2 =CHCH 2OCOCH 3 + H 2 O

C H 2= C H C H 2O C O C H 3 + H 2O C H 2= C H C H 2O H + C H 3C O O H

• Added benefit: The acetic acid produced in the 2nd reaction can be recovered and
used again for the 1st reaction, leaving no unwanted by-product.
Chemistry
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 Less Hazardous Chemical
Synthesis

Whenever practicable, synthetic

methodologies should be designed to use and
generate substances that possess little or no
toxicity to human health and the environment

Chemistry
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 Chemistry
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 Example 3 of green chemistry
• Production of styrene (=benzene ring with CH=CH2 tail)

• Traditional route: Two-step method starting with benzene, which is carcinogenic)

and ethylene to form ethylbenzene, followed by dehydrogenation to obtain styrene
C H 2C H 3
c a ta y st
+ H 2C = C H 2

e th y lb e n z e n e

C H 2 -C H 3 CH=CH 2

c a ta y s t

sty re n e
e th y lb e n z e n e

• Greener route: To avoid benzene, start with xylene (cheapest source of aromatics
and environmentally safer than benzene)

• Another option, still under development, is to start with toluene (benzene ring with
CH3 tail)
Chemistry
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 Less Hazardous Chemical Synthesis

Polycarbonate Synthesis: Phosgene Process

O
O
NaOH
HO OH + Cl Cl * O O n *

 Disadvantages
 phosgene is highly toxic, corrosive
 requires large amount of CH2Cl2
 polycarbonate contaminated with Cl impurities Chemistry
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 Less Hazardous Chemical Synthesis

Polycarbonate Synthesis: Solid-State Process

HO OH
O

+ * O O n *
O O

 Advantages
 diphenylcarbonate synthesized without phosgene
 eliminates use of CH2Cl2
 higher-quality polycarbonates
Chemistry
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 Reagents
• Phosgene, COCl2, is
commonly used as a starting
material for plastic polymers

• Phosgene is a highly toxic

substance, and the by-
products of many of its
reactions are undesirable.

A superior alternative
might be dimethyl
carbonate Chemistry
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 Designing Safer Chemicals

Chemical products should be designed to

preserve efficacy of the function while reducing
toxicity

Chemistry
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 Chemistry
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 Designing Safer Chemicals
Case Study: Antifoulants (Marine Pesticides)

Chemistry
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 Designing Safer Chemicals: Case Study: Antifoulants

Antifoulants are generally dispersed in the paint

as it is applied to the hull. Organotin compounds
have traditionally been used, particularly
tributyltin oxide (TBTO). TBTO works by
gradually leaching from the hull killing the fouling
organisms in the surrounding area

TBTO and other organotin antifoulants have long

half-lives in the environment (half-life of TBTO in
seawater is > 6 months). They also
bioconcentrate in marine organisms (the
concentration of TBTO in marine organisms to
be 104 times greater than in the surrounding
water).

Organotin compounds are chronically toxic to

marine life and can enter food chain. They are Chemistry
bioaccumulative. of the
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 Designing Safer Chemicals:
Case Study: Antifoulants
Rohm and Haas
Presidential Green Chemistry Challenge Award, 1996

The active ingredient in Sea-Nine® 211, 4,5-dichloro-2-n-octyl-4-

isothiazolin-3-one (DCOI), is a member of the isothiazolone family
of antifoulants

Chemistry
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 Designing Safer Chemicals:Case Study: Antifoulants

Sea-Nine® 211 works by maintaining a hostile growing environment for
marine organisms. When organisms attach to the hull (treated with DCOI),
proteins at the point of attachment with the hull react with the DCOI

This reaction with the DCOI prevents the use of these proteins for other
metabolic processes

The organism thus detaches itself and searches for a more hospitable
surface on which to grow

Only organisms attached to hull of ship are exposed to toxic levels of DCOI

Readily biodegrades once leached from ship (half-life is less than one hour
in sea water)
Chemistry
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 Safer Solvents and Auxiliaries

The use of auxiliary substances (solvents,

separation agents, etc.) should be made
unnecessary whenever possible and, when
used, innocuous

Chemistry
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 Chemistry
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 Safer Solvents
• Solvent Substitution
• Water as a solvent
• New solvents

Ionic liquids

Supercritical fluids

Chemistry
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 Safer solvents: Supercritical fluids

A SCF is defined as a substance above its critical temperature (TC) and critical
pressure (PC). The critical point represents the highest temperature and Chemistry
of the
pressure at which the substance can exist as a vapor and liquid in equilibrium. Environment
 Chemistry
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 Supercritical Carbon Dioxide (scCO2)
• Usually when liquids are heated they turn into a vapour and
when vapour is compressed it condenses into a liquid

• However, if a vapour is heated above a certain critical

temperature, the vapour cannot be liquefied no matter what
pressure is applied

• At these temperatures the distinction between liquid and gas is

blurred

• The material has similar properties to gas in that it expands to

fill any space, however, it also has similar properties to a liquid
and can be used as a solvent Chemistry
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• At this stage, the material is said to be a supercritical liquid
• Carbon dioxide forms a supercritical fluid at a pressure
of 73 atm and a temperature of 31°C

• This relatively low temperature makes superficial

carbon dioxide easy to work with

• Another useful feature is that its solvent properties can

be altered by making slight adjustments to
temperature and pressure

• scCO2 is an environmentally friendly option also

because it can be obtained as a by-product fromChemistry
other
of the
industries. It is also easy to recapture and rescue
Environment
 Chemistry
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 Design for Energy Efficiency
Energy requirements should be recognized
for their environmental and economic impacts
and should be minimized

Synthetic methods should be conducted at

ambient temperature and pressure

Chemistry
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 Chemistry
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 Heating
Cooling Global
Stirring Warming
Distillation
Compression
Pumping
Separation

Energy Burn fossil CO2 to

Requirement fuel atmosphere
(electricity)

Chemistry
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 Alternative energy sources: Photochemical Reactions

 Two commercial photochemical processes: From Cyclohexane

to Caprolactam process using NOCl → NO˙ + Cl˙ (535nm)

+ Cl + HCl

NO

+ NO

NO NOH.2HCl

+ 2 HCl

O
NOH.2HCl
N
Chemistry
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• Wavelengths between 1 mm and 1 m

Frequency fixed at 2.45 GHz

• More directed source of energy

• Heating rate of 10°C per second is achievable

• Possibility of overheating (explosions)

• Solvent-free conditions are possible

Chemistry
of the
• Interaction with matter characterized by penetration depth
Environment
 Use of Renewable Feedstocks

A raw material or feedstock should be

renewable rather than depleting whenever
technically and economically practical

Chemistry
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 Chemistry
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Converting D-glucose into lactic acid using certain
enzymes helps us to prepare aliphatic compounds
from lactic acid

E-coli converts D-glucose to catechol which acts as a

starting material for aromatic compounds

On the other hand isomaltulose which is widely

available in biomass can be converted into
glucosylmethyl furfural which can be used for
production of many heterocyclic compounds Chemistry
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Besides biomass cash crops is a new hope as
ethanol from sugarcane has been derived
successfully and now scientists are trying to use this
“bio alcohol” as a source of vehicle for future

Exhaust from Corn plant has been successfully

utilized for preparing bio-degradable plastic

Chemistry
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Raw Materials from Renewable Resources:
The Bio Fine Process

Paper mill
sludge O

HO

Agricultural O
residues,
Waste wood Levulinic acid

Municipal solid waste Chemistry

and waste paper of the
Environment
 Levulinic acid as a platform chemical
O
OH
HO O

OH butanediol
HO
HO
Acrylic acid
Succinic acid
O
O

O
O

HO

MTHF THF
(fuel additive) O
O

OH
H2N
CH3 O

O O
HO C C C C OH O
H2 H2 DALA (δ-amino levulinic acid)
(non-toxic, biodegradable herbicide)
Diphenolic acid Chemistry
gamma of the
butyrolactone Environment
Poly lactic acid (PLA) for plastics production

Chemistry
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 Polymers from Renewable Resources:
Polyhydroxyalkanoates (PHAs)
• Fermentation of glucose in the presence of bacteria and
propanoic acid (product contains 5-20% polyhydroxyvalerate)

• Similar to polypropene and polyethene

• Biodegradable (credit card)

OH

R O
O OH

O
Alcaligenes eutrophus n
HO OH propanoic acid
R = Me, polydroxybutyrate Chemistry
of the
R = Et, polyhydroxyvalerate Environment
OH
Polyhydroxyalkanoates (PHA’s)

Chemistry
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 Reduce Derivatives

Unnecessary derivatization (blocking group,

protection/deprotection, temporary modification
of physical/chemical processes) should be
avoided whenever possible

Chemistry
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 Chemistry
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 Protecting Groups

Two synthetic steps are added each time one is used

Overall yield and atom economy will decrease

“Protecting groups are used because there is no

direct way to solve the problem without them”

Chemistry
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 Catalysis

Catalytic reagents (as selective as

possible) are superior to stoichiometric
reagents

Chemistry
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 Chemistry
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• Using “green catalyst” is that its action mimics
nature in respect that all natural synthesis is
enzyme catalyzed reactions - Biocatalysts

• This not only helps in designing a

highly stereo specific, stereo selective and enantio -
selective product but also these reactions takes
place under ambient conditions

Chemistry
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 Biocatalysis

• Enzymes or whole-cell microorganisms

• Benefits

Fast rxns due to correct orientations

Orientation of site gives high stereospecificity

Substrate specificity

Water soluble

Naturally occurring

Moderate conditions

Possibility for tandem rxns (one-pot) Chemistry
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 Design for Degradation

Chemical products should be designed so

that at the end of their function they do not
persist in the environment and instead break
down into innocuous degradation products

Chemistry
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 Chemistry
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 Persistence
• Early examples:

Sulfonated detergents
 Alkylbenzene sulfonates – 1950’s & 60’s
 Foam in sewage plants, rivers and streams
 Persistence was due to long alkyl chain
 Introduction of alkene group into the chain increased
degradation

Chlorofluorocarbons (CFCs)
 Do not break down, persist in atmosphere and contribute to
destruction of ozone layer

DDT
 Bioaccumulate and cause thinning of egg shells Chemistry
of the
Environment
 Degradation of Polymers:
Polylactic Acid

 Manufactured from renewable resources

 Corn or wheat; agricultural waste in future

 Uses 20-50% fewer fossil fuels than conventional

plastics

 PLA products can be recycled or composted

Chemistry
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 Real-time Analysis for
Pollution Prevention

Analytical methodologies need to be further

developed to allow for real-time in-process
monitoring and control prior to the formation of
hazardous substances

Chemistry
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 Chemistry
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 Analyzing a Reaction

What do you need to know, how do you

get this information and how long does it take
to get it?

Chemistry
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 Inherently Safer Chemistry
for Accident Prevention

Substance and the form of a substance

used in a chemical process should be chosen
so as to minimize the potential for chemical
accidents, including releases, explosions, and
fires
Chemistry
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 Chemistry
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 Chemistry
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 Chemistry
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 Designing a
Green Synthesis
Chemistry
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Atom Economy
 The yield in a chemical reaction is satisfactory without the
formation of bi-products

 The reactions are focused to undergo addition reactions,

rearrangements or pericyclic reaction where a single product
is obtained which further increases the atom efficiency

For reactions whose desired product is a chiral compound

it is advisory to design such reactions which eliminates the

formation of racemic mixtures

Hence these type of synthesis should always be either Chemistry

highly
of the
Environment
stereo-specific or either highly stereo-selective
• (a) Use of “light” as a carrier of electrons which can eventually
reduce the usage of other chemical agents which act as a
carrier of electron and is obtained as waste products at the
end of a redox reaction

• (b) Eliminating the un-necessary use of protection-

deprotection methodologies

• (c) Replacement of soluble Lewis acids by mesoporous solids

containing bound sulphonates in green synthesis

Chemistry
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Use of Renewable Feedstocks
• Converting biomass into starting material

• D-glucose → Lactic acid → Aliphatic compounds

• D-glucose → Catechol → Aromatic compounds

• Isomaltulose in biomass → Glucosylmethyl furfural →

Heterocyclic compounds

• Ethanol from sugarcane → “Bioalcohol” as a source of

vehicle for future

• Exhaust from Corn plant → Bio-degradable plastic

Chemistry
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Use of Catalysts (Catalysis)
 Maximize the yield of the desired products by
developing such reactions which are catalyzed
reactions whose catalyst can be extracted and further
utilized for other reactions

 “Green Catalyst” → Enzyme catalyzed reactions

 Highly stereo specific, stereo selective and enantio -

selective product

 These reactions takes place under ambient

Chemistry
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conditions

Use of Green solvents
 Solvent in organic synthesis which is not only costly
but is very harmful for those who is handling them
also

 To minimize or eliminate these effects by using water

as a solvent or the super critical carbon dioxide

 Other super critical fluids used in green chemistry are

ethane, ethene, water, xenon etc
Chemistry
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Energy Efficiency
 Minimizing the energy requirements of industries by maximizing the
efficiency of chemical conversion and decreasing the activation energy of
the reactions by using recyclable catalysts can cut off the energy
requirement of industries by half or even more

 Eliminating the use of energy consuming steps like distillation,

crystallization, sublimation, ultra filtration etc

 Utilization of milder reaction conditions for carrying out a chemical reaction

 Incorporation of microwave energy which aims to achieve a high

temperature at much faster rates

 Utilization of ultrasonic energy for certain reaction can eventually solve this
Chemistry
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problem Environment
 Conclusion

Green chemistry not a solution to all

environmental problems but the most
fundamental approach to preventing
pollution
Chemistry
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 Chemistry
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 Chemistry
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