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• DEFINATION OF GREEN CHEMISTRY:

It is the use of chemistry for the


improvement of environmental condition like
pollution control, designing of good chemical
products and reduce the use of hazardous
substance.
• FATHER OF GREEN CHEMISTRY:

Paul T. Anastas
SUSTAINABLE DEVELOPMENT : It is
the development that meets the need of
present without compromising the ability of
future generation to meet their own need.
green chemistry helps to achive
sustainable development .
12 PRINCIPLE OF GREEN
CHEMISTRY
I) Prevention of waste or by products:
the main goal behind this is to
develop zero waste technology (ZWT) during
cleaning or treating of waste .
the another intention of this is to
use the waste or byproduct of one synthesis in
another as a raw material
• EXAMPLE :
I) The bottom ash of thermal power
station can be used as raw
material for cement and brick
industry
• EXAMPLE (II):Effluents comining out from
cleasing of machinery parts may be used as
coolant water in thermal power station
II)ATOM ECONOMY: It is a measure of amount of
atom in a starting material that should be present in
the mainproduct at the end of chemical process.

Good atom economy means , most of


the atoms are present in the desired product and
very less is left as byproduct so that lesser will the
waste disposable .

Atom economy gives the measure of


unwanted product in a process
• % Atom Economy =
formula weight of the desired product × 100
sum of formula weight of all the reactants
used in the reaction
EXAMPLE :
Conversion of Butan-1-ol to 1-bromobutane
CH3CH2CH2CH2OH + NaBr + H2SO4

CH3CH2CH2CH2-Br + NaHSO4 +H2O


• %Atom Economy =
mass of ( 4C + 9H + 1Br ) atoms × 100
mass of (4C + 12H + 5O + 1Br + 1S )atom
137u ×100
275u
= 49.81%
III) LESS HAZARDOUS CHEMICAL SYNTHESIS :
During any chemical reaction efforts
should be made to produce less hazardous chemical
and possibly more safe.
EXAMPLE:
DDT (dichlorodiphenyltrichloroethane) was
initially use as insecticides to prevent diseases like
typhoid and malaria which was carried by mosquitos
but this was harmful to living things and thus baned.
Now a days (BHC)benzenehexachloride is
used as insectisides,its γ-isomer is called linden or
gammexane.
DDT BHC
• IV)DESIGINING SAFER CHEMICALS : This
principle is similar to the previous.
main intension of this goal is to use less toxic raw
material to obtain safer products.
EXAMPLE: In polymer industries adipic acid is
widely used and benzene is the starting material use
for its preparation. But we should know that benzene
is volatile organic compound (VOC) and more over it is
carcinogenic.
therefore workers working in such industries are
more susistibile to the disease causing cancer
efforts have been made by Drath & Frost to
synthesis adipic acid from enzymatically from glucose.
ADIPIC ACID

BENZENE
• V) USE OF SAFER SOLVENTS & AUXILARIES:
The main intention behind this
principle is to use more safer solvents and
auxiliaries(ie green solvents) in every step of
reaction as these two can create the problem of
larger % of waste ,air pollution and other health
impact
EXAMPLE: In place of halogenated organic solvents
like CH2Cl2 , CHCl3 , CCl4 water or supercritial CO2 is
used to minimise it’s prolonged effect on worker .
VI) DESIGN FOR ENERGY EFFICIENCY :
During any chemical syntesis
minimum use of energy or to carry out the reaction
at normal room temperature and pressure is the
main intension of this principle .
This intension can be fluorised by
the use of catalyst , proper microbes and use
renewable materials.
EXAMPLE: in chemical synthesis refluxing
requires less energy, use of microwave heating and
deleloping such any more technologies.
VII) USE OF RENEWABLE FEED STOCK :
The main aim of this principle is to use renewable
resources like agricultural or biological products
and ensure a safe future. The products and waste
of renewable sources are biodergadable.
On the other hand nonreneable
sources put burden on enviroment.
EXAMPLE :
VIII) REDUCE DERIVATIVES (Minimization of
steps):
In many organic synthesis the use of
protecting group is involved but green chemistry
suggest the minimum use of these group because
these groups further needs deprotection for which
additional reagents are required and they can creat
waste .
Biocatalytic reaction are very often needs
no protection of selective groups.
NOT FOR EXAM
NOT FOR EXAM
Not for exam
Not for exam
Not for exam
IX) USE OF CATALYST :As we all know catalyst speedup
the rate of reaction ,thus we can say it’s an favourable step
in green chemistry .
It’s use actually reduce the time of rection, conserves
energy and minimise the waste.
EXAMPLE:
In Hydrogenation of oil Ni is used
In Habers process Fe is used.
In the manufacture of HDPE polymer{TiCl4+Al(C2H5)3}
In the manufacture of H2SO4 by contact process Pt is
used.
Fischer-Tropsch process (synthesis of gasoline)
Co for feedstock is natural gas & Fe for lower quality
feedstock like coal
X) DESIGN FOR DEGRADATION :
The main aim behind this principle to design such

chemicals which can degrade automatically so that

waste should no persist in environment .


XI) REAL-TIME ANALYSIS POLLUTION
PREVENTION:
For our present and future generation it is very
necessary to analyse and take proper care of
environmental pollution.
To fulfill this goal , chemical industries ,nuclear
reactors are continuously monitered.
XII) SAFER CHEMISTRY FOR ACCIDENT
PREVENTION :
This principle aims in the development
of such chemicals which minimize the risk of
chemical accidents like explosion ,fire and
emission.
EXAMPLE: if chemical process involve working
with gaseous substance then it’s risky since
they are volatile .
But working with nonvolatile
liquids and solids is more safer.
• Prevention of waste or byproducts.
• Atom Economy.
• Less hazardous chemical synthesis .
• Desigining of safer chemicals.
• Use of Safer solvents and auxilaries.
• Design for energy efficiency.
• Use of renewable Feedstock.
• Reduce Derivatives.
• Use of catalyst.
• Design for degradation.
• Real-time Analysis Pollution Prevention .
• Safer chemistry for Accident Prevention.
• THE ROLE OF GREEN CHEMISTRY
• INTRODUCTION TO NANOTECHNOLOGY
Nano:
Greek word which means dwarf
Extremely small
Nano meter scale one billionth of a
meter(ie 1nm=1x 10-9 m)
Nanoscale 1nm -100nm
Why Nano?
The materials we see around us are in bulk
material that possess macroscopic physical
properties
But materials synthesised at nanoscale
(1nm-100nm)possesses unique optical,
structural, thermal ,catalytic ,magnetic and
electrical properties.
These properties changes as a function of size
and are very different fron their bulk material
What is nanomaterial ?
Materials having structural component in the
range of 1nm-100nm are termed as
nanomaterials.
In fact nanomaterial are larger than single
atom but smaller than bacteria and cell.
These can be nanoparticles, nanowires, and
nanotubes .
Nanostructure materials may be organic
molecule, inorganic cluster metallic or
semiconductor particles.
defination : Nanotechnology is the
creation of useful material ,devices and
system at nanoscale by manipulation of
atoms or molecule.
It controls the matter at the length scale
of approximately 1 to 100 nanometers
What are Zero , One and Two dimensional
nanoscale system ?
 Zero dimensional structure
is the one which include all three .It means
that all the dimentions are measured within the
nanoscale.
eg. nanoparticles
 One-Dimentional Nanostructure:
One dimensional nanomaterials (1D)is
outside the nanoscale

Example:nanotubes, nanowires and nanorods


 Two-Dimensional Nanostructure :
Two dimensional nanomaterials are
also outside the nanoscale
Example: Thin films, plates like structure
graphene ,nanofilms ,nanolayers ,nanocoating.
• CHARACTERISTIC FEATURE OF
NANOPARTICALS:
COLOURS : It is an optical property of
nanoparticles
example gold has yellow shining colour
however if there are only 100 atoms arranged
in cube it’s colour would be much more red.
Bulk of gold does not exhibit catalytic
properties.
Au nanoparticles is an excellent low
temperature catalyst.
THE LYCURGUS CUP
• SURFACE AREA-to- VOLUME
RATIO
2
m
m
1
m
m

1mm

Surface Area(mm)=height x width x no of side x no of cubes


• For one cube For 8 cubes
• 2x2x6x1=24 1x1x6x8=48
Volume(mm) = height x width x length x no of cubes
• For one cube For 8 cubes
• 2x2x2x1=8 1x1x1x8=8
Surface Area / Volume Ratio
24:8=3 48:8=6
As surface to volume ratio increase
A greater amount of substance come in
contact with surrounding material
This results in better catalytic activity, since a
greater propertion of material is exposed for
potential reaction.
 SURFACE AREA-to- VOLUME RATIO
This is an important characteristic of
nanoparticles.
if a bulk material is subdived into a group of
nanoparticals then volume remains but the
collective surface area is largely increased
 due to which these small particles react much
faster because more surface area provides
more chemical reactivity
CATALYTIC ACTIVITY :
 Due to increase in surface area with
deacrease in particles size ,nanomaterial-
based catalyst show incresed catalytic activity.
 Catalyst used are heterogeneous catalyst ie
catalyst are in solid form and reaction occur
on the surface of catalyst
nanoparticle catalyst can be easily seperated
and can be recycled.
• EXAMPLE:Pd, Pt metal nanoparticals used in
hydrogenation reaction
• TiO2 , ZnO are used in photocatalysis
• Gold nanoparticles are found to be very good
catalyst for various organic reactions.
THERMAL PROPERTIES/MELTING
POINT:
All nanotubes are expected to have good thermal
property
It is said that carbon nanotubes are able to
transmit upto 6000 watts per meter per kelvin at
room temperature
 where as copper being a metal and well known
for it’s good thermal conductivity which transmit
385 watts per meter per kelvin .
 THERMAL PROPERTIES/MELTING POINT:
 The M.P of nanoparticals changes drastically
and depends on size .
for exmple :sodium of 1000 atoms melts at
288K 10,000 atoms melts at 303K and bulk
sodium melts at 371K.
• MECANICAL PROPERTIES:
Mecanical propertiesof nanomaterials
increases with decrease with size(but not
always)
Nanomaterials have less defects compared to
bulk materials which increase the mechanical
strength.
Nanomaterials with good mecanical strength
are stronger , harder , and more resistant to
corrosion
Eg used in sparkplugs ,microdrills
MECANICAL PROPERTIES :

For example nanosized copper and palladium


cluster with diameter in the size range of 5-7nm
can hardened upto 500% as compared to bulk.
• ELECTRICAL CONDUCTIVITY
The electrical properties of nanomaterials is
very different from bulk material.
Electrical conducyivity increases due to
surface scattering
Eg Nickel-metal hydride battries made of
nonacrystalline nikel and metl hyrdide require
far less frequent recharging and last much
longer.
ELECTRICAL CONDUCTIVITY:
Electrical conductivity is obsered to
change at nanoscale .
for example carbon nanotubes can act as a
conductor or semiconductor in behaviour
SYNTHESIS OF NANOMATERIALS
I)
• There are two approaches to sysnthesis
nanomaterialie Bottom Up and Top Down
• In bottom approach, molecular component
arrange themselves into more complex atom by
atom , molecule by molecule and cluster by
cluster from the bottom
• Example synthesis of nanoparticles by collidals
dispersion.
• In Top-Down approach , nanomaterials are
synthesized from bulk material by breaking the
material.
• The bulk solid are dis-assembled into finner
pieces until they are constituted of few elements.
• WET CHEMICAL SYNTHESIS OF NANOMATERIALS (sol-
gel process):
• Sol are dispersion of colloidal particles in a liquid.
• Colloids are solid particles with diameter 1-100nm .
• A gel is interconnected rigid network.
• A sol-gel process is based on inorganic polymerization
reaction .
• It is carried at room temperature and includes four
steps ie hydrolysis , polycondensation , drying and
thermal decomposition.
• This is widely used to prepare oxide materials.
• Formation of different stable solution of the
alkoxide or solvated metal precurcsor.
• Gelation resulting from the formation of an
oxide or alcohol-bridge network(gel) by a
polycondensation reaction .
• Aging of the gel means during that period gel
transforms into asolid mass.
• Drying of the gel: In this step , water and
other volatile liquids are removed from the gel
network.
• Dehydration: The material is heated at
temperature upto 8000C
• ANALYSIS OR CHARATERIZATION OF
NANOMATERIALS: The synthesised
nanomaterial is analysed by different tool and
technique.
• SCIENTISTS CONTRIBUTING TO NANOTECHNOLOGY:
The defination of nanotechnology was coined by
University Professor Nario Taniguchi in 1974
• HISTORY OF NANOTECHNOLOGY:
 Beautiful ruby red red colour of some ancient glass
panting is due to gold and silver nanoparticles trapped
in the glass matrix.
 The decorative glaze or metallic film known as lustre
found on some medieval pottery is due to certain
sperical metallic nanoparticles.
 Carbon black is a nanostructure material that is used in
tyres of cars to increase the life of tryes.(discovered in
1900).
 Carbon nanotubes are made up of graphite sheet with
nanosized diameter which have highest strength.
 Fumed silica,a component of silicon rubber ,coating,
sealants and adhesives is also a nanostructed material
• Application of Nanotechnology: It’s
application is widely based on their physical
,chemical ,optical,structural,catalytic properties
1. Nanoparticles can contribute to stronger , lighter ,
cleaner and smarter surfaces and systems, they are
used in the manufacturing of scratchproof
eyeglasses , transport ,sunscreen ,crack resistant
paints.
2. Used in electronic devices like (MRAM)
Magnetoresistive Random Acess Memory
3. It plays an important role in water purification
technique
4. It is widely employed in self cleanig technique
called as lotus effect.
How is nanotechnology use in water
purification?
 Water contains some waterborne pathogens like
virus and bacteria
 But most of the people are susceptible to
waterborne dieseases due to impure water.
 Thus to provide safe water is the present day
priority for which nonatechnology is more
helpful.
 Now a days cost effective filter maerials coated
with silver nanoparticals (AgNps) is used in
waterpurification
 Silver nanoparticles acts as highly effective as
bacterial disinfectant which removes E.coli from
water.
SELF-CLEANING (THE LOTUS EFFECT)
 The lotus plant (Nelumbo nucifera) is well known in Asia
for it’s exceptional cleanness
 Although it grows in mud water it’s leaves always appear
clean
 Lotus leaves are super hydrophobic ie drops of water roll
off free of residue taking away impurities with it.
 Investigation on their surface using reflection electron
microscopy (REM) shows that the surface is rough ,
contains many water repellent ,nanosized wax crystals (3D)
similar to small nipples and are in nanometer.
 These all combinations make lotus non-wettable or ultra
hyrophobic and posses self-cleaning property.
The principle of self-cleaning was discovered
in 1973 by the botanist Wilhem Barthlott
He for the first time implemented this
technique of surface self-cleaning in his
investigation and was successful and
registered the brand name as “lotus effect”
First commercial product made was silicon
resin used in house paints.
Later on it is also use in many fields like nano
tiles, arhitectural glass ,spray, polyesterfabric.

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