Gree

n
Chemist
ry
 Green Chemistry
• Introduction
• Percentage yield vs. atom economy
• The 12 principles of green chemistry
• Application of green chemistry in practice
• Feasibility of green chemistry for daily life
 Introduction
What is green chemistry?
• Green chemistry is the use of chemistry for
prevention of pollution problems. It involves the
design of chemical products and processes that are
environmentally benign. Green chemistry covers
all aspects and types of chemical processes that
reduce negative impacts to human health and the
environment.
• Green chemistry can be used in the following areas:
• Aerospace
• Agricultural
• Automotive
• Biotechnology
• Ceramics and Materials
• Chemical
• Communications
• Computer Systems
• Consumer Products
• Dyes and Photography
• Educational
• Electronics and Electrical Equipment
• Environmental
• Food and Beverage
• Homeland Security
• Leather
• Medical
Percentage yield and
atom economy
 Percentage yield
It does not indicate how efficiently the
reactants have been used in generating the
desired product.

% Yield = Actual yield x 100%

Theoretical yield
 Calculating Percentage (%) Yield
2.3g of sodium reacts with an excess
of chlorine to produce 4.0g of sodium chloride.
What is the percentage yield?
2Na(s) + Cl2(g) ⇒ 2NaCl(s)
(Ar reactants: Na=23 Cl=35.5 Mr product: NaCl= 58.5)

2.3g Na = 2.3 mol Na = 0.1 mol Na

23

Theoretically 0.1 mol Na should yield 0.1 mol NaCl

Theoretical yield of NaCl = 58.5 x 0.1 = 5.85g

% Yield = Actual yield x 100% = 4.0g x 100% = 68%

Theoretical yield 5.85g
 Calculating Percentage (%) Yield
If 1.2g of magnesium reacts with an excess
of oxygen to produce 0.8g of magnesium
oxide…
What is the percentage yield?
2Mg(s) + O2(g) ⇒ 2MgO(s)
(Ar reactants: Mg=24 O=16 Mr product: MgO= 40)

1.2g Mg = 1.2 mol Mg = 0.05 mol Mg

24
Theoretically 0.05 mol Mg should yield 0.05 mol MgO
Theoretical yield of MgO = 40 x 0.05 = 2g

% Yield = Actual yield x 100% % Yield = 0.8g x 100% = 40%

Theoretical yield 2g
 Calculating Percentage (%) Yield
If 2g of calcium carbonate reacts with an excess of hydrochloric
acid to produce 1.11 g of calcium chloride….

What is the percentage yield?

2HCl + CaCO3 ⇒ H2O + CO2 + CaCl2
(Mr values are: CaCO3 = 100 CaCl2 = 111)

2g CaCO3 = 2 mol CaCO3 = 0.02 mol CaCO3

100
Theoretically 0.02 mol CaCO3 should yield 0.02 mol CaCl2
Theoretical Yield of CaCl2 = 111 x 0.02 = 2.22g

% Yield = Actual yield x 100% % Yield = 1.11 x 100 = 50%

Theoretical yield 2.22
 2008-Al Chem Paper II
5(a) Upon irradiation of visible light, 0.450g of 2-4-
dimethylpentane undergoes monochloro-substitution to gives
0.200g of 1-chloro-2,4-dimethylpentane. 0.167g of 2-chloro-2,4-
dimethylpentane and 0,117g of 3-chloro-2,4-dimethylpentane.
(ii)(I) calculate the overall percentage yield for the monchlorinated
products formed.

ANS
Total no. of moles of monochloroinated products
= (0.2+0.167+0.117)/134.5
= 3.60X10-3
No. of moles of 2-4-dimethylpentane = 0.45/100
= 4.5X10-3
Overall % yield = 3.60X10-3/4.5X10-3
= 80
 1998-Al Chem Paper I
8(b) 20.0g of 4-nitrobenzoic acid reacted with PCl5 to give a
product which reacted exothermically with ammonia to
give T. After treatment with Br2 and NaOH(aq), T gave a
soild. Crystallization of the soild from ethanol gave 9.3 g of
U( C5H6N2O2)
(i)Calculate the % yield of U from 4-nitrobenzoic acid

ANS
Molar mass of C7H5NO4 =167.12
Molar mass of C5H6N2O2 = 138.128
% yield = 9.3X 167.12 X100%
20.0X138.128
= 56.3%
 Sustainable Development and Atom Economy

Yield is not enough, because it

•Ignores auxiliaries (reagents,

catalysts, solvents, etc.)
•Ignores work-up and purification
•Ignores energy used, hazards
involved, and any toxic chemicals
used or produced.
 Sustainable Development and Atom Economy
Developing chemical reactions with a high atom economy is
therefore crucial in moving towards sustainable development.
High atom economy also makes good economic sense. However,
some chemical reactions have a limited atom economy because:

 the reaction may be reversible (the reactants might not be

converted completely into the products)

 the reaction may produce unexpected products

 the products cannot be efficiently separated from the reactants

Sustainable Development and Atom Economy

The atom economy is measure of the conversion

of starting material (reactant) into desired
product. It is different from percentage yield.

In an ideal reaction, all the atoms of the reactants

would end up as useful product. Such a reaction
would produce no waste at all, but this is rarely
possible.
 Calculating Atom Economy

The atom economy (also called atom utilisation) of a reaction, is a

measure of the percentage of the starting materials that actually
end up as useful products.

The atom economy can be calculated in the following way:

% atom economy = mass desired product(s) x 100%

total mass of reactants
 Calculating Atom Economy

In the production of ammonium nitrate...

NH3(g) + HNO3(aq) ⇒ NH4NO3(aq)

ammonia + nitric acid ⇒ ammonium nitrate

…17g of NH3 and 63g of HNO3 produce 80g of NH4NO3

Calculate the atom economy for this reaction:
NH3= 17g HNO3 = 63g NH4NO3 = 80g
Atom economy = 80g x 100 = 100%
80g
As there are no waste products in this reaction, it has an atom
economy of 100%.
 Calculating Atom Economy
Example 2:
In the smelting of iron:

2Fe2O3(s) + 3C(s) ⇒ 4Fe(s) + 3CO2(g)

iron oxide + carbon ⇒ iron + carbon dioxide
…for every 320g of iron oxide 224g of iron is produced.
Calculate the atom economy for this reaction:
2Fe2O3= 320g 3C= 36g 4Fe= 224g 3CO2 = 132g
Atom economy = 224g x 100 = 63%
320 + 36g
As the reaction produces carbon dioxide as a waste product, the
reaction can not have an atom economy of 100%. The atom
economy of this reaction could be improved, if a use could found
for the waste carbon dioxide.
 Atom Economy and Percentage Yield

Nitrogen reacts with hydrogen to make ammonia.

N2 + 3H2  2NH3
a) Calculate the maximum theoretical mass of ammonia that
can be made by reacting 90g of hydrogen with an excess of
nitrogen.
b) In the reaction, only 153g of ammonia was produced.
Calculate the percentage yield.
c) Calculate the atom economy to make ammonia from the
reaction of nitrogen and hydrogen.
 a) Calculate the maximum theoretical mass of ammonia that can be made
by reacting 90g of hydrogen with an excess of nitrogen.
number of moles of H2 = 90/2 = 45moles
number of moles of NH3 = 2/3 x 45 = 30 moles
Maximum theoretical mass
= 30 x (14+3) = 510 g

b) In the reaction, only 153g of ammonia was produced. Calculate the

percentage yield.
Percentage yield = (153/510) x 100% = 30%

c) Calculate the atom economy to make ammonia from the reaction of

nitrogen and hydrogen.
Atom economy = 100% (since all the reactants converts to products)

Conclusion:
High atom economy is not equal to high percentage yield.
Reaction Type Description Atom Economy

Addition Different molecules join together 100% as all reactant atoms end up
to make a new substance in the product

Condensation Two molecules join, with the Always a little less than 100% as
production of a small molecule small molecules are produced,
like water or ammonia which are usually waste.
Elimination A group of atoms is removed Generally poor because an
from a molecule, usually leaving additional product is always
a double or triple bond formed
Rearrangement Atoms are rearranged to create 100% as the same atoms are
a different substance with the present in the product as in the
same empirical formula reactant

Substitution A group of atoms on a molecule The group replaced creates a

is replaced by a different group product too, but as this may vary
considerably, substitutions can be
from fairly good to very poor
The 12 principles of green chemistry
In 1998, the 12 principles of green chemistry were
articulated by Anastas, P. T. & Warner, J.C. in the book
‘Green Chemistry: Theory and practice.’

1. Prevent waste
2. Design safer chemicals and products
3. Design less hazardous chemical syntheses
4. Use renewable feedstocks
5. Use catalysts, not stoichiometric reagents
6. Avoid chemical derivatives
7. Maximize atom economy
8. Use safer solvents and reaction conditions
9. Increase energy efficiency
10. Design chemicals and products to degrade
after use
11. Analyze in real time to prevent pollution
12. Minimize the potential for accidents
Applications of
green chemistry
 Microscale Experiment
• a teaching method
widely used at
school and at
university levels,
working with small
quantities of
chemical
substances
• use low-cost and
even no-cost
material
 Advantages of Microscale
Experiment
• less starting materials are required for testing the possibility of
some unknown reactions
• very useful when the starting materials are very expensive
• less reactant, less reagent and less solvent are required
• lower cost
• save time and money
• use small amount of reactants can make the experiment more
safe
• less chemical waste is deposited
 Disadvantages of Microscale
Experiment
• equipment and textbooks about microscale experiment are
• but the costs can be recovered in a relatively short period
of time due to savings realized on purchase and disposal
costs of reduced quantities of chemicals
 Use of hydrogen peroxide as a
bleaching agent
• Traditional chlorine bleach
-
(active ingredient – hypochlorite OCl )
• Disadvantages:
1. Toxic chlorine gas may evolve
2NaOCl + 2NH3  2NaONH3 +Cl2
2. Poisonous chlorinated organic compounds may be found
3NaOCl +NH3  3NaOH +NCl3
3.The reaction of byproducts hydrazine and
monochloramine is highly exothermic
NH3 + NaOCl  NaOH + NH2Cl
NH3 + NH2Cl + NaOH  N2H4 + NaCl +H2O
• Bleached by oxidation :
H2O2(aq) + dye  H2O(l) + (dye+O)

Applications:
• bleaching agent for hair
• the bleaching of pulp for paper manufacturing
• household disinfectant

• Hydrogen peroxide should be stored in a cool, dry, well-

ventilated area and away from any flammable or
combustible substances, it should be stored in a container
composed of non-reactive materials such as stainless steel
or glass
 Use of fuel cell
• It is a device that converts fuel i.e.
hydrogen into electrical energy
• The cell, the reactants flow in and
products flow out electrolyte in the
presence of electrolytes such as
H2SO4
• The anode and cathode are coated
with Pt, which acts as a catalyst.
+ -
At anode : 2H2  4H +4e
- +
At cathode : O2 + 4e + 4H  2H2O
• The elctrons produred at the anode flow through the
wire connecting the external circuit, electrical energy is
generated
• At the end, pure water and heat are produced.

Advantages of using H-cell:

• they are environmentally friendly
• no air pollutants are emitted
• do not contribute to global warming as combustion of
fossil fuel is not involved
• high efficiency
• hydrogen is the most plentiful element in the universe
Applications of H-cell:
• fuel cell vehicles (still in development stage)
• electrical system of rockets and shuttles
 Manufacture of nylon-6,6 by
Beckmann rearrangement

oxime lactam Monomer

for nylon-6
• a typical Beckmann rearrangement
• The oxime from cyclohexanone has identical carbonyl
substituents and exists as a single isomer
• The product of the rearrangement is a lactam (a cyclic
amide), which can be hydrolyzed to an omega-amino acid
• This lactam serves as an important industrial precursor
to nylon-6
Advantages
• no wastage
• water is a renewable source
• rearrangement – 100% atom economy
Obtain saturated fats by catalytic
hydrogenation
• adds hydrogen atoms at the double bonds of a fatty acid
chain to produce an artificial fatty acid
• operate at pressures of 3 – 6 atm and temperatures of
100 – 180oC
• using nickel / palladium / nickel / rhodium as catalysts
Advantages of using catalytic hydrogenation
• cheaper than animal source fats
• are available in a wide range of consistencies
• increased oxidative stability
• longer shelf life
• a harder consistency
• a higher melting point
• better oxidation stability
 Ionic liquid

Fig. 1 Examples of simple room temperature ionic liquid

• Ionic liquid is used to refer to a molten salt that is a

liquid at ambient temperatures. They generally are
compounds that have both a large anion and cation, and
possess a low degree of symmetry.
Ionic liquids can be:
• simple salts, or
• binary ionic liquid

Example
• 1-alkyl-3-methylimidazolium tetrafluoroborate salts are
miscible with water at 25 °C where the alkyl chain is less
than 6, but at or above 6 carbon atoms, they are form a
separate phase when mixed with water.
• This makes solvent extraction easier.
Advantages
• Prevent waste
• Use renewable feedstocks
• Use catalysts, not stoichiometric reagents
• Avoid chemical derivative
 Biofuels
• Fuels derived from organic biomass from recently living
animals or plants or their byproducts, has transformed
from a niche alternative to fossil fuels.

• Vegetable oils, animal fats, ethanol and biodiesel are

biofuels.
• Landfill sites generate gases by anaerobic digestion.
Landfill gas contains approximately 50% methane, the
gas found in natural gas.

• Ethanol is produced by enzyme digestion fermentation

of the sugars, distillation and drying.
Advantages
• Prevent waste
• Use renewable feedstocks
• Design chemicals and products to degrade after use
Haber process in the manufacture of
ammonia
• Area: Chemical + Ceramics and Materials
• N2(g) + 3 H2(g)  2 NH3(g) (ΔH = −92.4 kJ·mol−1)
• catalyst: a form of magnetite, iron oxide
• Preparation:
• First, methane is cleaned to remove sulphur impurities
that will poison the catalysts.
• Steam reforming: over a catalyst of nickel oxide
(CH4 + H2O → CO + 3 H2 )
• Secondary reforming: addition of air to convert the
methane that did not react during steam reforming.
CH4 + O2 → 2 CO + 4 H2
CH4 + 2 O2 → CO2 + 2 H2O
• Then the water gas shift reaction yields more hydrogen
from CO and steam.
CO + H2O → CO2 + H2
• Last step: the gas mixture passing into a methanator,
which converts most of the remaining CO into methane
for recycling as carbon monoxide poisons the catalyst
CO + 3 H2 → CH2 + H2O
Use of supercritical carbon dioxide
(e.g. decaffeinating coffee)

Critical temp.
(31.1 °C) and critical
pressure
(72.9 atm/7.39 Mpa)
are low
• In a fluid state while also being at or above both its
critical temperature and pressure
• Yields rather uncommon properties, e.g. dissolving
organic substances
• Low toxicity and environmental impact
• An important commercial and industrial solvent
• It replaces a chlorinated organic solvent
tetrachloroethene (Cl2C=CCl2) which may cause cancer
in dry cleaning, metal cleaning and other polluting
industrial processes.
 H2O2 and O2 as environmentally
benign oxidising agents
• Many industrial processes involves oxidising agents, e.g.
KMnO4, K2Cr2O7, conc. NHO3, etc.
• These oxidising agents are not green.
• Conc. NHO3 on reduction produces toxic N2O, which
induces greenhouse effect and leads to ozone depletion

• H2O2 is one of the green replacement for these harmful

oxidisng agents
• Aqueous hydrogen peroxide is an ideal oxidant, because
the atom economy is excellent and water is the only
theoretical side product
H2O2  [O] + H2O or 2H2O2  O2 + 2H2O

• Example
• Cyclohexane is converted directly to pure, crystalline
hexanedioic acid in a very high yield
• Molecular oxygen is another environmental benign
oxidising agent which has been used industrially, e.g.

O2, catalyst, sunlight

RCH2OH RCOOH

• The product from the reduction of O2 is environmentally

benign water
 Bioplastic
• Bioplastics (also called organic plastics) are a form of
plastics derived from renewable biomass sources, such as
vegetable oil, corn starch, or microbiota, rather than fossil-
fuel plastics which are derived from petroleum.
• On the other hand, bioplastic can be made from
agricultural byproducts and also from used plastic bottles
and other containers using microorganisms.

Plastics made from corn are

already on the market.
Advantages of bioplastic:
• Because of their biological degradability, the use of
bioplastics is especially popular for disposable items,
such as packaging and catering items.
• In these areas, the goal is not biodegradability, but to
create items from sustainable resources.
• The production and use of bioplastics relies less on fossil
fuel as a carbon source and also introduces fewer
greenhouse emissions if it biodegrades. They
significantly reduce hazardous waste caused by oil-
derived plastics, which remain solid for hundreds of
years.
Disadvantages of bioplastic:
• There are fears that bioplastics will damage existing
recycling projects.
• Shelf life is limited because the plastic is permeable to
water - the bottles lose their contents and slowly deform.
Catalytic converter
 Catalytic converter
• used to reduce the toxicity of emissions from an internal
combustion engine
• used on generator sets, forklifts, mining equipment, trucks,
buses, trains, and other engine-equipped machines
• provides an environment for a chemical reaction wherein
toxic combustion by-products are converted to less-toxic
substances
 Catalytic converter
Types of catalytic converter:
• Two-way
• Three-way
 Two-way catalytic converter
• There are two simultaneous tasks :
• Oxidation of carbon monoxide to carbon dioxide :
2CO + O2 → 2CO2
• Oxidation of unburnt hydrocarbons (unburnt and
partially-burnt fuel) to carbon dioxide and water :
CxH2x+2 + 2xO2 → xCO2 + 2xH2O
• (a combustion reaction)
• Widely used on diesel engines to reduce hydrocarbon and
carbon monoxide emissions
• However, cannot control amount of nitrogen oxides NOx
 Three-way catalytic converter
• There are three simultaneous tasks :
• Reduction of nitrogen oxides to nitrogen and oxygen :
2NOx → xO2 + N2
• Oxidation of carbon monoxide to carbon dioxide :
2CO + O2 → 2CO2
• Oxidation of unburnt hydrocarbons (HC) to carbon
dioxide and water :
CxH2x+2 + 2xO2 → xCO2 + 2xH2O
 Three-way catalytic converter
• Three-way catalytic converters can store oxygen from the
exhaust gas stream, when the air fuel ratio goes lean
• When oxygen is insufficient, the stored oxygen is released
and consumed
• Unwanted reactions : formation of hydrogen sulphide and
ammonia
• But can be limited by precious metals used
• Nickel or manganese is added to block the adsorption of
sulphur by the washcoat
 For diesel engines
• Most commonly used catalytic converter is the diesel
oxidation catalyst
• They uses excess O2 in the exhaust gas stream to oxidize
CO to CO2 and HC to H2O and CO2
• Reach 90% efficiency, eliminate diesel odor and help to
reduce visible particulates (soot)
• However they are incapable of reducing NOx
 Catalyst Poisoning
• Catalyst poisoning occurs when the catalytic converter is
exposed to exhaust containing substances that coat the
working surfaces
• catalyst cannot contact and treat the exhaust
• The most notable contaminant is lead, so vehicles equipped
with catalytic converters can only be run on unleaded
gasoline.
• Other common catalyst poisons : manganese, silicon,
phosphorus, zinc
 Treatment for Catalyst Poisoning
• Catalyst poisoning can sometimes be reversed by running
the engine under a very heavy load for an extended period
of time
• The increased exhaust temperature can sometimes liquefy
or sublimate the contaminant, removing it from the
catalytic surface
• However, removal of lead deposits in this manner is
usually not possible due to lead's high boiling point
 Potential applications
(1) Corn waste converted to chemicals
• conversion of glutamic acid to -aminobutyric acid
(GABA) (nitrogen-containing)using a decarboxylase
enzyme
• producing nitrogen-containing industrial chemicals
more cheaply than the energy intensive from the waste
from bioethanol production
• improving the green credentials and the economics of
biofuel production
(2) Expanding waste to reduce waste
• expanding the structure of waste polyvinyl-alcohol
(PVA) from liquid crystal display (LCD) screens to form
a mesoporous material with a high surface area
• use of enzyme immobilisation, tissue scaffolds or drug
delivery due to the biocompatibility of PVA
• providing an exciting new method for recovering
materials that would otherwise go to waste
• iodine, which is present in waste PVA, is essential for the
expansion process
 Feasibility of green chemistry for
daily life applications
• A number of difficulties involves:
• Chemical (what technologies are available?)
• Economic (who pays, who benefits?)
• Social (who are affected?)
• Political (who is responsible?)
• Possible contribution of green chemistry in achieving
sustainability in the 21st century:
• (1) Renewable energy technologies
E.g. Array of solar cells to supply electric power to space
shuttle
• (2) Reducing our dependence on the dwindling fossil
carbon
• (3) The replacement of existing polluting technologies by
environmentally benign alternatives
Past Paper
Analysis
(05, 07, 08)
 Past Paper 05 II 5.(a)(iii)

Besides cutting down petroleum

consumption, suggest one additional
advantage of using the alternative fuel over
using gasoline. (1M)
 Past Paper 05 II 5.(a)(iii)
 Additional Information:
• Gasoline (petrol) is commonly used as motor car fuel.
• Lead petrol: Straight chain alkanes cause knocking
( 死火 ) in the engine when they are burnt as oxygen
is used up very quickly for complete combustion.
• The problem is solved by adding tetrathyllead (TEL)
>> leaded petrol (Toxic to human, was ban by the HK
government since 1994.)
• Unlead petrol: Straight chain alkanes >> branched
chain
 Past Paper 05 II 5.(a)(iii)
Ans:
Alternative fuel produces less
air pollutants than petroleum
when burn.
Past Paper 07 I 8.(a)(i)

(2M)
 Past Paper 07 I 8.(a)(i)
Ans:
Past Paper 07 I 8.(a)(ii)

(1M)
 Past Paper 07 I 8.(a)(ii)
Ans:
Past Paper 07 I 8.(a)(iii)

(1M)
 Past Paper 07 I 8.(a)(iii)
Ans:
 Past Paper 08 I 10.

10. Write an essay on the application of the

principles of green chemistry in industry.

(20M)
Ans: Past Paper 08 I 10.
Ans: Past Paper 08 I 10.
 Past Paper 08 I 10.
 Additional Information:
• Supercritical carbon dioxide:
• carbon dioxide that is in a fluid state while also
being at or above both its critical temperature and
pressure, yielding rather uncommon properties
• usually as a gas in air at standard conditions for
temperature and pressure / as a solid called dry ice
when frozen
 Past Paper 08 I 10.
 Additional Information: Phase diagram
 Past Paper 08 I 10.
 Additional Information:
- if temperature & pressure are both increased from
standard conditions for temperature and pressure to
be at or above the critical point for carbon dioxide
>> adopt properties midway between a gas and a liquid
- behaves as a supercritical fluid above its critical
temperature (31.1 °C) and critical pressure (72.9 atm),
expanding to fill its container like a gas but with a
density like that of a liquid
 Past Paper 08 I 10.
 Additional Information:
- low toxicity and environmental impact
- is becoming an important commercial and industrial
solvent
- relatively low temperature of the process and the
stability of CO2 also allows most compounds to be
extracted with little damage or denaturing
 Past Paper 08 I 10.
Ans:
 Past Paper 08 I 10.
Ans:
End of presentation