Green Chem - Week 1-4 - Full-2023!09!20-Lecture (Student)

Green Chemistry
Dr. Nguyễn Đăng Khoaa, Dr. Lê Vũ Hàa, Dr. Hồ Hoàng Phướcb

a Faculty of Chemical Engineering, Ho Chi Minh City University of Technology,
Vietnam
b Chemical Engineering, Competence Centre for Catalysis, Chalmers University of
Technology, Sweden
Contact: khoand1989@hcmut.edu.vn, lvha@hcmut.edu.vn, phuoc@chalmers.se
Off-line appointments (applied to the whole course): 9:00 – 10:00 Wednesday, 11:00 – 12:00 Thursday at 211B2
Short introduction to the lecturers
To-do list
Objectives of the course
Assessment methods
Course rules
Group building
Content of the course
2023-08-25 Chalmers University of Technology 2

COURSE OBJECTIVES
- To understand the current role of chemical industry in

our society and economy as well as the impact of
chemical industry on ecosystem.
- Present principles of green chemistry
- Apply the green-chemistry principles to improve simple

chemical processes
3
Distribution Assessment methods
Assignments (personal/group, in class/at home/presentation):
+ Calculation
40% + Viewpoint and discussion
+ Given topics
+ Given articles
Final examination
+ Multiple-choice
+ Short answer
60%
+ Long explanation
+ Calculation
+ Allowed paper materials

Course rules
+ Mandatory attendance in class (checked by assignments)
+ Close to your group (for group assignments)
+ Free to give any questions/problems/comments/solutions in class
+ Correct understanding of the introduced concepts after each chapter
+ Active to access the course
+ Confident to show your opinion and weakness
+ Careful to consider aspects
+ Kind to our planet

Group building
+ CC01: 4 members per group
+ CC02: 3 members per group

Contents
Overview modern chemistry
Impact of chemical industry to environment
12 principles of Green Chemistry
Catalysis for Green Chemistry
Solvents, reactors, renewable materials
Some examples of Green Chemistry

Time Planned Content
Week 1 Introduction to Green Chemistry

Week 2
Week 3 The 12 principles of green chemistry
Week 4
Week 5
Week 6 Green improvements of chemical production: Catalysis
Week 7
Week 8
Week 9 Green improvements of chemical production: Solvents
Week 10
Week 11 Green improvements of chemical production: Reactors

Week 12
Green improvments of chemical production: Renewable materials
Week 13
Week 14 Green improvement of industrial processes: Some examples

Week 15 Summarization
Texbook
1) P.C. Anastas and J.C. Warner ‘Green Chemistry Theory and Practice’, Oxford University Press, New York, 1998
2) M. Lancaster, GREEN CHEMISTRY: An Introductory Text, University of York, RSC, 2002

Do you know? Where are they from?
2019
https://youthtimemag.com/where-the-worlds-garbage-goes-the-journey-of- https://sisu.ut.ee/waste/book/11-definition-and-classification-waste
trash/

https://cen.acs.org/content/dam/cen/static/pdfs/cen90th-timeline.pdf

Quiz game
1. Thomas Midgley Jr. discovered that tetraethyllead can be an antiknock additive to gasoline. At the same year, Acids and Bases got
refined definitions from Johannes N. Bronsted and Thomas M. Lowry, another from Gillbert N. Lewis. When was it?
a) 1914 b) 1923 c) 1925 d) 1939
2. Dupont chemists invented nylon. In the same year, ICI patented the process for polyethylene (PE). When was it?
a) 1915 b) 1925 c) 1935 d) 1945
3. When was industrial-scale catalytic petroleum cracking (setting the stage for modern oil refinery) developved?
a) 1927 b) 1937 c) 1947 d) 1957
4. Thomas Midgle led the effort to use this compound as refrigerant to replace NH3, CH3Cl, and SO2 in 1920s. In 1941, at an ACS
meeting, he took the stage and inhaled a lungful of this compound and blew out a candle to prove that this compound is nontoxic and
nonflammable. What is it?
a) CFCs b) Ar c) N2O d) CO2
5. The U.S. exploded first atomic weapon in Alamogordo in 1945 and dropped two bombs over Japan to end World War II. Who was
the father of atomic bomb program?
a) Albert Einstein b) Werner Heisenberg c) Harry S. Truman d) J. Robert Oppenheimer
6. In 1955, the scientists of one company developed the first fluoride-containing toothpaste shown to prevent cavities. What is the
name of this company?
a) Procter & Gamble (P&G) b) Uniliver c) BASF d) Dow chemicals
7. When was a hole in Earth’s atmospheric ozone layer first observed over Antarctica?
a) 1965 b) 1975 c) 1985 d) 1995
8. When did FDA (Food and Drug Administration in the USA) approve azidothymidine (AZT) to treat HIV/AIDS?
a) 1987 b) 1997 c) 2007 d) 2017
9. IBM researchers improved the resolution of atomic force microscopy so much that they were able to visualize all of the atom
position and bonds of a single molecule for the first time. When was it?
a) 1989 b) 1999 c) 2009 d) 2019
10. The Chernobyl nuclear power plant in the Soviet union has a reactor core meltdown, releasing massive amounts of radiation. 25
years later, Fukoshima Daiichi nuclear power plant (Japan) suffered major damage from the magnitude 9.0 earthwake and tsunami.
When did these event happen?
a) 1980, 2005 b) 1986, 2011 c) 1978, 2003 d) 1953, 1978
How chemistry contributes to the modern world?
1910

Daily life without products of the chemical and related industries?
▪ Transportation – production of gasoline and diesel from

petroleum, fuel additives for greater efficiency and reduced
emissions, catalytic converters, plastics to reduce vehicle weight
and improve energy efficiency.
▪ Clothing – man-maded fibres such as rayon and nylon, dyes,
water-proofing and other surface finishing chemicals.
▪ Sport – advanced composite materials for tennis and squash
rackets, all-weather surfaces
▪ Safety – lightweight polycarbonate cycle helmets, hire-retardant
furniture.
▪ Food – refrigerants, packing, containers and wraps, food
processing aids, preservatives.
▪ Medical – artifical joints, ’blood bags’, anaesthetics, disinfectants,
anti-cancer drugs, vaccines, dental fillings, contact lenses,
contraceptives.
▪ Office – photocopying toner, inks, printed circuit boards, liquid-
crystal displays.
▪ Home – material and dyes for carpets, plastics for TVs and
mobile phones, CDs, video and audio tapes, paints, detergents.
▪ Farming – fertilizers, pesticides

Petroleum-derived products
✓ Fuels
✓ Electronics
✓ Textiles
✓ Sporting Goods
✓ Health & Beauty Products
✓ Medical Supplies
✓ Household Products
https://www.capp.ca/oil/uses-for-oil/
Everyday on the news: Crude oil price? Elemental composition of one crude oil
One barrel = 159 L = 42 galons

Demand for petrochemical feedstocks will continue to grow
Quiz: how many refinery does Vietnam have by 2022?

a) 0 b) 1 c) 2 d) 4
https://www.esyekta.com/en/products/petroleumproducts
Standard Recommended
S level (ppm)
Euro 2 < 500
Euro 3 < 350
Euro 4 < 50
Euro 5 < 10 Ultra low sulfur diesel
Euro 6 < 10
TCVN 5689:2005 stipulated the maximum sulfur content of diesel oil to _______ppm?
a) 2000 b) 500 c) 350 d) 50

Natural sources
Bulk chemicals/ Fine Customers of

Speciality
Commodity chemcials
Basic chemicals chemicals chemicals chemical industry
• Olefins • Plastics & Engineering Resins
• Active pharmaceutical • Automotive/Transportation
ingredient • Synthetic fibers
• Rubber Products • Consumer products
• Aromatics • Peptides
• Paints & Coatings • Packing
• Proteins
• Chlor-Alkali • Adhesives & Sealants
• Building & construction
(Chlorine, caustic soda) • Alkaloids
• Lubricants
• Sport/Recreation
• Methanol • Biocides • Water treatment products
• Industrial
• Solvents, etc. • Cleaning products
• Others • Medical
(e.g. NH3, phosphorus) • Industrial chemicals
• Pharmaceuticals
• Others
✓ Starting material other chemicals ✓ High purity • Personal care
✓ Blends of two or • Textiles
✓ High demand ✓ Low volume production more fine • Electrical/electronics
✓ High volume production (<1000 tons/year) chemicals
• Aircraft/aerospace
✓ Continous process ✓ Batched process
✓ Low price • Business equipment
✓ High cost (>10$/kg)
https://www.spglobal.com/commodityinsights/en/ci/research-analysis/q23-formula-for-success-in-the-chemical-industry-analyzing-energy-at-the-extremes.html
Crude oil Synthesis gas, methanol, ammonia, lubricants,
(cyclo)alkanes, aromatics, naphtenes, aromatic
Natural gas Petrochemical industry acids, ketons, esters, mercaptanes, thiophenes,
Coal asphaltenes, fuel+ >> 100 others
Naphtha, styrene Poly-

Vinyl Chloride ethylene, propylene, esters, styrene,
Polymer industry amides, urethane, carbonates, acryl
C2H4, C3H6, etc isocyanate (resins & paints)
Metals, Chlor-alkali
Air Sulfur → sulfuric acid
Ores Inorganic chemicals Nitrogen → Nitric acid
Mineral salts Phosphorus → phosphoric acid
Ammonia, inorganic bases/salts
Artificial fertilizers
Air Pesticides as:
Natural feedstock Agro chemicals fungicides
Organic chemicals herbicides
insecticides
bactericides
Fine chemicals > 10000 chemicals
Natural gas, Coal

Fuel oil, Renewable Power generation Electricity
sources

Give names of 10 international chemical companies that you
know?
Give names of 5 domestic chemical companies (in Vietnam)

that you know?

https://www.chemistryviews.org/top_ten_chemical_companies_in_2021/
https://vietnamcredit.com.vn/news/top-5-largest-chemical-companies-in-vietnam_14641

Which chemicials are involved in making fertilizers?
Can you guess top 5 of the most common used in chemical industry?
https://www.essentialchemicalindustry.org/98-chemicals.html

Environmental Pollutants
A pollutant is a harmful material that can enter the biosphere through the land, air, or water
In early stage of chemical industry, some products were commonly used without recognization
of the product toxicity
DDT

DDT ▪ 1939 known as a wonder chemical due to its insecticidal
properties and the discovery were even awarded Nobel prize for
Swiss chemist Paul Hermann Müller in 1948
▪ 100000 tonnes per annual by 1960s
• DDT was a broad spectrum insecticide.

• It was effective in combating malaria,
typhus, and other insect-borne diseases.
• DTT was widely utilized in livestock
production, crop control, forestry, and even
home gardening.
controlling
outbreaks of
typhoid
Colorado beetle Housefly malaria-carrying mosquitoes

https://blog.restek.com/?p=6324
DDT was used in the military to DDT aerial delivery to protect

prevent soldiers in the fields forestry against harmful insects.
from contracting insect-borne
diseases.
http://www.publicdomainfiles.com/show_file.php?id=135157 Image Source:
51817026 https://en.wikipedia.org/wiki/Spruce_budworm#/media/File:195
5._Fort_tri-
motor_spraying_DDT._Western_spruce_budworm_control_proj
ect._Powder_River_control_unit,_OR._(32213742634).jpg

Unintended Consequences of DDT
1960’s: Evidence of environmental and toxicological effects.
1972: US EPA issues cancellation orders of DDT.
Today…
• DDT exposure and reproductive effects in humans is suspected.
• DDT is now classified as a Persistent Organic Pollutant (POP).
• DDT is currently classified as a probable carcinogen.
Currently DDT:
• is known to be very persistent in the environment.
• will accumulate in fatty tissues of animals.
• can travel long distances in the atmosphere, which leads to increased exposure.
• After the use of DDT was discontinued, its concentration in the environment and
animals has decreased. However, because of its persistence in the environment,
DDT degraded residues from wide spread use still remain.
Source: Center for Green Chemistry and Green Engineering at Yale

Which one is the most common used plastic?

Name 10 countries?

Energy sources
Vietnam final total energy consumption by sector in 2012

❖ Can you give names of some electricity sources in Vietnam?
❖ Which one is the main source?

Energy sources
Coal, natural gas
Thermal power plant
Hoa Binh Tra Vinh Ninh Thuan
Hydropower plant Non-hydro renewables (wind, solar)

Thermal power plants
Coal
combustion
This graph shows how electricity is generated from thermal power plant using coal.
a) Describe the principle
b) Guess what kinds of chemical elements can be existed in coal?
c) What are possible pollutants that are realsing from the plant?
https://www.eia.gov/energyexplained/coal/coal-and-the-environment.php
Impact of thermal power plants
Particulate matter Smog, haze, and respiratory illnesses, lung disease
Coal CO2 Primary greenhouse gas
combustion SO2 Acid rain and respiratory illnesses
NOx (NO, NO2) Smog, haze, and respiratory illnesses, lung disease
https://www.eia.gov/energyexplained/coal/coal-and-the-environment.php
xxx
Mercury
and other
heavy
metals

Is there any thermal power plant in your home town?

If possible, search and share the names of 10 thermal power plants in Vietnam?

Question 1: How many thermal power plants using coal did Vietnam have till 2022?
a) 20 b) 25 c) 39 d) 61
Question 2: In May 2020, Vietnam
imported 5.1 million tons of coal (see the
Figure). Assume that this coal contains 2
wt% of S, 50 wt% of C, around 30% ash,
and others (H, N,O). If all of 5.1 million
tonnes of coal was used in the thermal
power plant, and we assume that the
combustions of C and S in air have the
conversion of 100% while ash is not
combusted and will be discarded as solid
waste.
a) Write the combustion reaction of C and S with assumption that carbon dioxide and sulfur dioxide are the
product of the combustion.
b) Calculate the amount of CO2 and SO2 as well as solid waste (in tonnes) which were emitted from these
combustion processes
https://www.reuters.com/markets/commodities/vietnams-coal-emissions-primed-surge-after-imports-jump-maguire-2023-07-
12/#:~:text=Coal%20accounted%20for%20an%20average,increased%20overall%20coal%2Dfired%20output.
Impact of transportation vehicles
(3-17%) 98-99% cleaner

(2-12%)
(2-12%)
(some of 0.1%)
✓ CO
✓ Hydrocarbons
✓ NOx (NO + NO2)
✓ Particulate matter (PM)
23-26 Nov 1966
✓ Particulate number (PN)
✓ SOx and others
https://dieselnet.com/tech/emi_intro.php
• > 60 millions motorcycles registered in Vietnam by 2019

• Cars
• Trucks
• Bus, airplanes
• Construction vehicles, marine ships
Impact of industrial parks
Quiz: how many industrial parks are there in Vietnam up to 2022?

a) ~200 b) ~300 c) ~400 d) ~500
List some of industrial parks that you know
➢ Waste water
➢ Solid waste
➢ Air pollution
Water pollutants
➢ Detergents ➢ Solvents/Dyes
➢ Volatile Organic Compounds ➢ Petroleum hydrocarbons
➢ Food processing waste ➢ Lubricants
https://www.unido.org/sites/default/files/2017-06/Eco-Industrial_Park_Vietnam_Brochure_0.pdf
Biology, Miller Levine, Prentice Hall, Textbook (chapter 6-2)
Impact of Industrial pollutions
Personal Local Global
▪ Physiological ▪ Damage the natural ▪ Acid rain
▪ Psychological environment and ▪ Global warming
▪ Pathological effects ecosystems ▪ Greenhouse gas effect
▪ Diseases ▪ Ozone depletion
▪ Smog

Acid rains
pH = -log [H+] HNO3 0.01 M

pH = -log [10-2] = 2
Clean rain: pH 5.6 (why?)
CO2 + H2O ⇌ H+ + HCO3-

HCO3− ⇌ H+ + CO32−
Burning fossil fuels SO2, NO, NO2

SO2 + OH· → HOSO2·
HOSO2· + O2 → HO2· + SO3
SO3 (g) + H2O (l) → H2SO4 (aq)
NO2 + OH· → HNO3
SO2 (g) + H2O ⇌ SO2·H2O

SO2·H2O ⇌ H+ + HSO3−
HSO3− ⇌ H+ + SO32−
SO2 + 1/2O2 → SO3 NO + 1/2O2 → NO2

SO3 + H2O → H2SO4 2NO2 + O2 + H2O → HNO2 + HNO3
https://www.epa.gov/acidrain/what-acid-rain
Impact of Acid rains
Materials Forests/Lands
Acid rains
Acquatic life
Human health
This figure illustrates the pH level at which key organisms may
be lost as their environment becomes more acidic. Not all fish,
shellfish, or the insects that they eat can tolerate the same
amount of acid.
https://www.epa.gov/acidrain/what-acid-rain
Greenhouse gas effect
Can you explain the green house gas effect?

Can you give names of some green house gases? Where do they come from?
Did you know?
Without naturally occurring greenhouse gases, the earth would be too cold to support life as we know it.
Without the greenhouse effect, the average temperature of the earth would be about -19°C rather than the
14°C we currently experience.
https://www.eia.gov/energyexplained/energy-and-the-environment/greenhouse-gases.php
Greenhouse gas effect
•Carbon dioxide (CO2)

Several major greenhouse gases that •Methane (CH4)
result from human activity
•Nitrous oxide (N2O)
•Industrial gases:
• Hydrofluorocarbons (HFCs)
• Perfluorocarbons (PFCs)
• Sulfur hexafluoride (SF6)
• Nitrogen trifluoride (NF3)
https://www.eia.gov/energyexplained/energy-and-the-environment/greenhouse-gases.php
Source: IPCC (2014) Exit based on
global emissions from 2010
Every greenhouse gas has its own global warming potential (GWP), which is a measurement of how much heat the GHG can trap
within the atmosphere and how much of an environmental impact it is expected to have. Specifically, GWPs determine the ratio of
heat trapped by one unit mass of the specific GHG to that of one unit mass of carbon dioxide over a specified time period.
CO2 equivalent = GWP*GHG emission (tons)

In which GWP = global warming potential
factor
https://www.ipcc.ch/site/assets/uploads/2018/02/ar4-wg1-chapter2-1.pdf
Global warming:
➢ Rising temperatures
➢ Rising sea levels
➢ Unpredictable weather patterns
➢ Increase in extrememe weather events
➢ Land degradation
➢ Loss of wildlife and biodiversity
e.g. predict the disappearance of Mekong delta by the year 2100
Record in the hotest summer 2022 in Europe
Nature Communications, 10, Article number: 3847 (2019)
• General pollution in the 1960s and 1970s for the developing countries
• Water pollutions → unsuable for drinking, cooking, cleaning, swimming, and other activities
• Pollutants includes chemicals, trash, bacteria, and parasite
Disposal of untreated waste Eutrophication Foaming river

water
In many counties, the chemical industry is often viewed, by the general public, as causing more
harm than good. A major reason is that the industry is perceived as being polluting and causing
significant environmental damage.
Image Source:
https://commons.wikimedia.org/wiki/File:DISCOLORED_WATER_IN_FOREGROUND_IS_FROM_SEWAGE_DISCHARGED_INTO
_THE_CUYAHOGA_RIVER_BY_THE_CITY_PUMP_STATION_-_NARA_-_550214.jpg
There were many things being dumped in the

river such as: gasoline, oil, paint, and metals.
The river was called "a rainbow of many
different colors".
Some river! Chocolate-brown, oily, bubbling
with subsurface gases, it oozes rather than
flows. "Anyone who falls into the Cuyahoga
does not drown," Cleveland’s citizens joke
grimly. "He decays.”
-Time Magazine, August 1969
“In June 1969, the Cuyahoga River in Cleveland, Ohio caught fire — a river long polluted with oily
wastes, chemicals, and debris. The river fire, coming at a time of emerging national concern over
pollution, made big news and became something of a famous disaster”
The Bhopal pesticide plant of Union
Carbide India Limited,
Date 2 December 1984 – 3 December 1984

Time (UTC+05:30)
What do you see? Can you guess what happened?

Methylamine (1) reacts with phosgene (2) to
produce methyl isocyanate (3), which in turn
reacts with 1-naphthol (4) to yield carbaryl (5)
https://en.wikipedia.org/wiki/Bhopal_disaster
Source: Center for Green Chemistry and Green Chemical Engineering at Yale
Poison gas leaked from a Union Carbide factory (Bhopal, India) killing thousands instantly and injuring many
more (many of who died later of exposure). Up to 20,000 people have died as a result of exposure (3-8,000
instantly). More than 120,000 still suffer from ailments caused by exposure.
How did this happen?
• Methyl isocyanate - used to make pesticides - was being stored in large quantities on-site at the plant.
• Methyl isocyanate is highly reactive, exothermic molecule.
• Most safety systems either failed or were inoperative.
• Water was released into the tank holding the methyl isocyanate.
• The reaction occurred and the methyl isocyanate rapidly boiled, producing large quantities of toxic gas.

Need actions!!!
▪ The EU is a committed member of United Nations climate

negotiations
Under the Paris agreement, the EU committed in 2015 to cutting greenhouse gas emissions in the EU by at
least 40% below 1990 levels by 2030. In 2021, the target was changed to at least 55% reduction by 2030
and climate neutrality by 2050.
▪ The European Green Deal: achieving zero net emissions by 2050
▪ Cutting greenhouse gas emissions with EU climate policies
▪ Boosting renewable energies and energy efficiency

▪ Creating a sustainable and circular economy by 2050
The EU’s Circular Economy Action Plan includes measures about:
➢ Packaging and plastics

➢ Sustainable textiles
➢ Electronics and ICT
➢ Construction and buildings Vietnam?
➢ Batteries and vehicles
➢ The food chain
➢ Critical raw materials
➢ Repairing and reusing goods

Milestones in the development of the green chemistry concept
1969 Report of the secretary-General of the United Nations (U. Thant): Problems of the
Human Environment
For the first time, threats to civilization resulting from irrational use of resources and environmental
degradation were presented
1972 Report of the Club of Rome: The Limits of Growth
Forecasts regarding the future of civilization based on statistical models were presented. Attention was
paid to the need to change the approach in the use of environmental resources in order to maintain
ecological balance
1972 United Nations Conference on the Human Environment – the Stockholm Conference
(1st Earth Summit)
For the first time, the term ”sustainable development” was used and its basic assumptions were given:
Man has the basic right to freedom, equality and appropriate living conditions in the environment. Good
quality of the environment allows you to live in dignity and prosperity. Therefore, man bears great
responsibility for protecting the environment and improving its condition for present and future generations
1987 Report of the Brundtland Comission: Our common Future

Premises for the concept of sustainable development (eco-development). The paradigm of sustainable
development: meeting the needs of the present generations without compromising the ability of the future
generations to meet their needs.
1992 Rio Declaration on Environment and Development (2nd Earth Summit).
1998 2001 2003

12 Principles of Green Principles of Green 12 Principles of Green
Chemistry Chemical Technology Engineering
2013 Principles of Green Analytical Chemistry
2023-09-20 Chalmers University of Technology

Chemsuschem 2018, 11, 2845-2858 49
Future Growth of Green Chemistry Market
Future of Green Chemistry is ”green”

Haber – Bosch process
CH4 + H2O → CO + 3H2 CO + H2O → CO2 + H2

The only scientific achievement recognized by two
2CH4 + O2 → 2CO + 4H2 Nobel Chemistry awards, given in 1918 to Fritz Haber
and in 1931 to Carl Bosch
WGS
Reforming Partial oxidation

Hydrogen production
Laboratory scale usually focuses on yield (conversion) for comparision purpose
• Various resources Other source of H2?
• Many processes
• Catalysts
• Separation processes
Energy efficiency?
• Heat transfers
• Release CO2 Alternative process?
Measures of Reaction Efficiency
Reaction: A + B → P (main product) + W (unwantted materials)
1 mole 4.5 mole Maleic anhydride Waste
1 mole benzene + 4.5 mole oxygen → Stochiometry
1 mole benzene + 5.0 mole oxygen → excess oxygen → product is calculated with benzene
1 mole benzene + 4.0 mole oxygen → excess benzene → product is calculated with oxygen
In a chemical reaction, the limiting reagent is the reactant that determines how much of the
products are made.
✓ A or B → the limiting reagent →depending on the starting amounts used

✓ The reactant that isn’t the limiting reagent → leftover unused materials
Let’s remember:
At standard
temperature (0 oC) and
pressure (1 atm) (STP)
n = m/M n = V/22.4
Example:
Mw = SO2 = 32+16x2 = 64
Example: at STP
If m = mass = 3.2 g of SO2 V (SO2) = 1.12 L
→ n = 1.12/22.4 = 0.05 mole
→ n = 3.2/64 = 0.05 mole
Let’s Practice:
If we mix 1g of acetic acid and 1g of NaOH and there is a reaction as below:
Which one is the limiting reagent, acetic acid or NaOH? Calculate:
a) The reacted amount of each compound if the limiting reagent is completely converted
b) The unreacted amount of the reagent which is not the limiting reagent
Acetic Acid NaOH Sodium Acetate Water

Mass (g) 1g 1g - -
MW (g mol-1) 60 40 82 18
Mole (mol)
The Limiting Reagent? ______________
Mole (mol)
reacted
Mole (mol)
un-reacted Source: Center for Green Chemistry and Green Engineering at Yale
Let’s Practice:

Mass (g) 1g 1g - -
MW (g mol-1) 60 40 82 18
Mole (mol) 0.0167 0.025
Acetic acid
The Limiting Reagent? ______________
Transformed/
Reacted 0.0167 0.0167
amount (mol)
Mole (mol)
un-reacted
0 0.0083
Conversion of NaOH?
It is defined:
Transformed quantity of substrate A = 0.0167/0.025 x 100 = 66.7%
Conversion (%) = x 100
Total amount of substrate A
Keep in mind that in real case, the conversion of limiting reagent is not always 100%
Theoretical Yield
Theoretical Yield (g): the amount of product (g) that would result
if all the limiting reagent reacted/went to full completion.
Let’s do the math:

Mass (g) 1g 1g - -
MW (g mol-1) 60 40 82 18
Mole (mol) 0.0167 0.025 ? ?
The Limiting Reagent? ____Acetic Acid_____ Theoretical Yield? Theoretical Yield?

Theoretical Yield
Theoretical Yield (g): the amount of product (g) that would result
if all the limiting reagent reacted/went to full completion.
Let’s do the math:

Mass (g) 1g 1g - -
MW (g mol-1) 60 40 82 18
Mole (mol) 0.0167 mol 0.025 0.0167 0.0167
The Limiting Reagent? ____Acetic Acid_____ Theoretical Yield: Theoretical Yield:
82 x 0.0167 18 x 0.0167
= 1.37 g = 0.30 g

Percent Yield
Percent Yield: The actual yield divided by the theoretical yield,

expressed as a percentage.
Actual Yield: The quantity of product that actually results from a

reaction.
actual yield
Percent Yield = × 100
theoretical yield

Percent Yield
So what is the percent yield of this reaction if the actual yield was 0.5g of
sodium acetate?

Mass (g) 1g 1g - -
MW (g mol-1) 60 40 82 18
Mole (mol) 0.0167 mol 0.025 0.0167 mol 0.0167 mol
Theoretical Yield: Theoretical Yield:
The Limiting Reagent? ____Acetic Acid_____ 82.034 x 0.0167 18.02 x 0.0167
= 1.37 g = 0.30 g
actual yield 0.5

Percent Yield = × 100 = × 100 = 36.5%
theoretical yield 1.37
Selectivity of a product
Cu catalyst
CO + 2H2 CH3OH (1)
Methanol synthesis
CO + 3H2 CH4 + H2O (2)
When the reaction has more than one product → selectivity concept
The selectivity is the ratio of the amount of a desired product P obtained and the
amount of a limiting reactant converted.
Actual quantity of the target product achieved

% Selectivity = x 100
Transformed quantity of substrate A

= x 100
Inital quantity of substrate A – leftover quantity of substrate A

Cu
catalysts
CO + 2H2 CH3OH (1)
Methanol synthesis 5.76 g
CO + 3H2 CH4 + H2O (2)
0.448 L
Example: 5.376 L 26.88 L
In methanol synthesis process, a gas mixture of 5.376 L CO and

26.88 L H2 is fed into the reactor and after reaction, in the outlet
stream, there are 5.76g CH3OH and 0.448 L of CH4.
All gas volumes are at the standard condition.
What is the selecitivity of methanol and methane in this process?

Cu
catalysts
Methanol synthesis CO + 2H2 CH3OH (1)
5.76 g
from CO
CO + 3H2 CH4 + H2O (2)
0.448 L
5.376 L 26.88 L
CO H2 CH3OH CH4
Volume L 5.376 26.88 - -
MW (g mol-1) 28 2 32 16
Initial Mole (mol) nCO = nH2 = - -
The Limiting Reagent? ___
Reaction 1 nCO (1) = nCH3OH (1) =
Reaction 2 nCO (2) = nCH4 (2) =
nCO reacted nCO (1) + nCO(2)
Selectivity / %

Cu
catalysts
Methanol synthesis CO + 2H2 CH3OH (1)
from CO 5.76 g
CO + 3H2 CH4 + H2O (2)
0.448 L
5.376 L 26.88 L
CO H2 CH3OH CH4
Volume L 5.376 26.88 - -
MW (g mol-1) 28 2 32 16
Initial Mole (mol) 5.376/22.4 = 0.24 26.88/22.4 = 1.2 - -
The Limiting Reagent? ___
Reaction 1 nCO (1) = 0.18 nCH3OH (1) = 0.18 mol
Reaction 2 nCO (2) = 0.02 nCH4 (2) = 0.02 mol
nCO reacted 0.20
Selectivity / % = 0.18 / 0.2 x 100 = 90%
0.02 / 0.2 x 100 = 10%

Reaction: A + B → P (main product) + U (unwantted materials)
In which A is a limiting reagent (get consumed first in a chemical reaction)

Conversion (%) = x 100


% Yield = x 100
Theoretical quantity of products achievable
Yield (%) = Conversion (%) x Selectivity (%)/100
~ 100%: quantitative, > 90%: excellent, > 80%: very good, > 70%: good, > 50%: fair, and < 40%:
poor
C + O2 → CO2 95% selectivity
C + O2 → CO 5% selectivity Excellent or not?
Measures of Reaction Efficiency Reaction: X + A → P (main product) + U (unwantted materials)

Conversion (%) = x 100%
In 2014, the largest manufacturer of automotive vehicle airbags, Takata, recalled millions of
their airbags. Did you know that the deploying of an air bag is chemistry! The chemical
reaction that takes place is as follows:
N = 14
NaN3(s) ➔ Na(s) + 1.5N2(g) Na = 23
The driver-side airbag would contain a canister containing
about 50 grams of sodium azide. Assuming that during one
accident test (reaction happens), the N2 gas volume
produced from the reaction is approximately 25 L at the
standard condition.
Calculate the conversion (%) of the reaction.
50 g NaN3 → initial mole of NaN3 = 50/65 = 0.769 mol. Conv = 0.744/0.769 x 100
25 L at STP → mole N2 produced=25/22.4= 1.116 mol = 96.7%
→ mole NaN3 reacted = 1.116/1.5 = 0.744
Ethylene glycol: coolant, heat transfer agent
Reaction: X + A → P (main product) + U (unwantted materials)
C4H6O4 118 C3H6O3 90

2H2 CH3OH
Dimethyl oxalate (DMO) Methyl glycolate

(MG)
4H2 2CH3OH
Ethylene glycol 62
Dimethyl oxalate (EG) C2H6O2
Example:
In one experiment, 59 g of dimethyl oxalate (DMO) was loaded into a
batch reactor → at the end of the reaction (around 190 oC), the mixture
H H-H contains only 24.8 g of EG and 4.5 g of MG. Let’s calculate:
a) Conversion of DMO
H3C-O-C-C-O-CH3
=
=
b) Selectivity of EG
OO
H c) Yield of EG
Dimethyl oxalate
C4H6O4 + 2H2 → C3H6O3 + CH3OH (1)
C4H6O4 + 4H2 → C2H6O2 + 2CH3OH (2)
In one experiment, 59 g of dimethyl oxalate (DMO) was loaded into a batch reactor → at the end of the
reaction (around 190 oC), the mixture contains only 24.8 g of EG and 4.5 g of MG. Let’s calculate:
a) Conversion of DMO State DMO MG EG
Before reaction nDMO = - -
c) Yield of EG
After reaction nDMO = nMG = nEG =
nDMO (1) = Theoretical amount of

nDMO (2) = EG can be formed =
nDMO reacted =
Calculation Conv% DMO = Sel% (EG) =
Yield% (EG) =

C4H6O4 + 2H2 → C3H6O3 + CH3OH (1)
C4H6O4 + 4H2 → C2H6O2 + 2CH3OH (2)
In one experiment, 59 g of dimethyl oxalate (DMO) was loaded into a batch reactor → at the end of the
reaction (around 190 oC), the mixture contains only 24.8 g of EG and 4.5 g of MG. Let’s calculate:
a) Conversion of DMO State DMO MG EG
Before reaction nDMO = 59/118 = 0.5 mol - -
c) Yield of EG
After reaction nDMO = nMG = 4.5/90 = 0.05 nEG = 24.8/62 = 0.4
nDMO (1) = nMG = 0.05 Theoretical amount of

nDMO (2) = nEG = 0.4 EG can be formed
nDMO reacted = 0.05 + 0.4 = =nDMO reacted = 0.45 mol
0.45 mol
Calculation Conv% DMO = Sel% (EG) =
0.45/0.5x100 = 90% 0.4/0.45x100=88.9%
Yield% (EG) =
0.4/0.5x100 = 80%
(1)
C6H5COOK + HCl → C6H5COOH + KCl (2)
Yield of benzoic acid synthesis is 55%. To produce 122 g of product:
a. How many gram of starting materials ?

b. How many gram of waste products ?
Hint → write a total reaction (1) + (2)

C6H5COOK + HCl → C6H5COOH + KCl
Yield of benzoic acid synthesis is 55%. To produce 122 g of product:
a. How many gram of starting materials ?

b. How many gram of waste products ?
Actual quantity of product achieved

% Yield = x 100% Theoretical quantity (benzoic acid) =
Theoretical quantity of products achievable 122/55*100 = 221.8 g
158 92 36.5 122 18 56 87 74.5

2KMnO4 + C6H5CH3 + HCl → C6H5COOH + H2O + KOH + 2MnO2 + KCl
2x1.818x158 1.818x92 1.818x36.5 221.8 g

n = m/M
= 221.8/122
808.1 g 586.3 g
= 1.818 mol
Chemical plant Production of maleic anhydride
Maleic anhydride is a chemical intermediate that can be used in

several applications in nearly every field of industrial chemistry. The
main end use is related to the production of unsaturated polyester
resins. Its name is also associated with certain agrochemicals, dye
products, and plasticizers Encyclopedia of Toxicology (Third Edition)
2014, Pages 138-141
Energy Energy
Materials Product Product

Reactor
Purification
(feedstocks) T, P Byproduct
Waste
Catalyst Solvent
Designing an Ideal Green Reaction
• Feedstock: Benzene
Toxic? Safe to deliver? Alternative?
• Product: anhydride maleic
• Atom efficiency (carbon efficiency)
• Waste
• Catalyst
• Solvent
• Energy efficiency
• Safe plant
What is green chemistry?
The design of chemical products & processes that reduce or
eliminate the use or generation of hazardous substances
“Green Chemistry is a revolutionary approach to the way that products are

made; it is a science that aims to reduce or eliminate the use and/or
generation of hazardous substances in the design phase of materials
development.”
– John Warner, Co-Founder of Green Chemistry
https://www.acs.org/greenchemistry/principles/12-principles-of-green-chemistry.html
Anastas, P. T., Warner, J. C. (2000). Green chemistry: Theory and Practice. New York; Oxford University Press.

The 12 Principles of Green Chemistry
2
1. Waste Prevention 2KMnO4 + C6H5CH3 + HCl → C6H5COOH + H2O + KOH + 2MnO2 + KCl
2. Atom Economy
3. Less Hazardous Chemical Synthesis. 3 1
4. Designing Safer Chemicals.
5. Safer Solvents and Auxiliaries.
4
6. Design for Energy Efficiency.
No DDT
7. Use of Renewable Feedstocks.
8. Reduce Derivatives. Less steps
9. Catalysis.
10. Design for Degradation. Biodegradation plastic
11. Real-time Analysis for Pollution Prevention.
12. Inherently Safer Chemistry for Accident Prevention.
No more Bhopal accident
Anastas, P. T., Warner, J. C. (2000). Green chemistry: Theory and Practice. New
York; Oxford University Press.

1. Waste Prevention The principles address:

• Toxicity
2. Atom Economy
- Reducing the hazard
3. Less Hazardous Chemical Synthesis.
• Feedstocks
4. Designing Safer Chemicals. - Use of renewable resources
5. Safer Solvents and Auxiliaries. • Designing safer products
- Non-toxic products by design
• Biodegradability
7. Use of Renewable Feedstocks. - Enhancing breaking down at the end of life
8. Reduce Derivatives. • Energy
9. Catalysis. - Reducing the energy needs
• Accidents
10. Design for Degradation.
- Eliminating accidents
11. Real-time Analysis for Pollution Prevention. • Efficiency
12. Inherently Safer Chemistry for Accident Prevention. - Shorter processes and synthesis

Benefits of Green Chemistry
• The environment: Products which will biodegrade and

won’t persist in the environment
• Human health: Products with won’t cause

toxicity to humans
• The economy: Novel products which boost

competitiveness
• For sustainability: Products made from

renewable resources
• For science: Fundamental new insights

Risk& Environmental
1. Waste Prevention Waste Energy Materials Plant
Hazard
VOCs
impact
Cost
2. Atom Economy
4. Designing Safer Chemicals.
5. Safer Solvents and Auxiliaries.
7. Use of Renewable Feedstocks.
8. Reduce Derivatives.
9. Catalysis.
11. Real-time Analysis for Pollution Prevention.
12. Inherently Safer Chemistry for Accident Prevention.
Read the 12 principles and try to fill in the Table with the
number of each principle which is relevant to each title.
When you finish, then look at the graph and correct yourself
Anastas, P. T., Warner, J. C. (2000). Green chemistry: Theory and Practice. New
York; Oxford University Press.

1. Waste Prevention The principles address:

• Toxicity (3, 4, 5, 7, 10)
2. Atom Economy
- Reducing the hazard
• Feedstocks (3, 7)
4. Designing Safer Chemicals. - Use of renewable resources
5. Safer Solvents and Auxiliaries. • Designing safer products (3, 4, 5, 7, 10)
- Non-toxic products by design
• Biodegradability (4, 7, 10)
7. Use of Renewable Feedstocks. - Enhancing breaking down at the end of life
8. Reduce Derivatives. • Energy (1, 2, 6, 8, 9)
9. Catalysis. - Reducing the energy needs
• Accidents (3, 4, 5, 11, 12)
- Eliminating accidents
11. Real-time Analysis for Pollution Prevention. • Efficiency (1, 2, 6, 8, 9)
12. Inherently Safer Chemistry for Accident Prevention. - Shorter processes and synthesis
Can you connect the principles (on the left side) that are
relevant to each section on the right side?

1. Prevention (Waste or Pollution): It is better to prevent waste than to treat
or clean up waste after it has been created
A+B P+W
Ways to prevent waste?
1. Avoid the generation of W.

2. Find alternatives to A & B to improved overall efficiency of a
reaction.
3. Incorporate better catalysts to push the reaction to full
completion
▪ Historical reason → closure of a phloroglucinol plant at Océ Andeno (later to become part of DSM Fine Chemicals)
▪ The cost of disposing of the waste was rapidly approaching the selling price of the product
Phloroglucinol manufacture from TNT
Phloroglucinol is a spasmolytic
agent to treat colic, as well as
spastic pain of the digestive
and biliary tracts
This process generated ca. 40 kg of solid waste containing Cr2(SO4)3, NH4Cl, FeCl2 and KHSO4 for every kg of phloroglucinol.
Example of E-factor
▪ Roger Sheldon proposed E-factor in late 1980s → Environmental Factor (kg waste/kg
desired product)
The lower your E-Factor, the better
E-factor = total waste (g) / product (g)
performing your product is
158 92 36.5 122 18 56 87 74.5

2KMnO4 + C6H5CH3 + HCl → C6H5COOH + H2O + KOH + 2MnO2 + KCl
E-factor = (56+18+87*2+74.5)/122 = 2.64
Annual production
Industry sector E-factor Waste produced (t)
(t)
Oil refining 106-108 Ca. 0.1 105 – 107
Bulk chemicals 104-106 <1–5 104 – 5 × 106
Fine chemicals 102−104 5–50 5 × 102 − 5 × 105
Pharmaceuticals 10–103 25–100 2.5 × 102 − 105
Sheldon, R. Chem Tech, 1994, 24, 38

Example of E-factor
Benzen oxidation
(1)
C6H6 C4H2O3
E-factor = (2 x 44+2x18)/98 = 1.27
(2)
C4H8
E-factor = 3x18 / 98 = 0.55
Which reaction is better from E-factor point of view? (2)

Example of E-factor
Friedel-Craft Alkylation (Substitution)

All numbers represent the mass of the chemical after the reaction
2 2 + 2 HCl
By product
159 g
Main product By product
Phenol Chloroethane Catalyst Solvent 2-Ethylphenol Waste? E-factor Total waste

(not recyled) for 3 tons of
products
194 g 129 g 5g 1200 159 g =1528-159 =1369/159 =25.8 tons
= 1369 g = 8.6
Input = 1528 g = Output

Mass balance rule → mass of all input materials = mass of all output materials
Case study: Production of ethylene oxide
Ethylene oxide is used as an intermediate in the production of several industrial

chemicals, the most notable of which is ethylene glycol. It is also used as a
fumigant in certain agricultural products and as a sterilant for medical equipment
and supplies.
Conventional ethylene oxide synthesis

included:
• A 2-step synthesis with a chlorohydrin
intermediate.
• For each kilogram of product, 5 Kg of
waste were disposed.

Case study: Production of ethylene oxide
Alternative production of ethylene oxide:

• Use of molecular oxygen removes the
need for chlorine.
• New process generates more than 16
times less waste than the original one,
and eliminates the formation of
waste water.
1/2
E-factor = 0.3
(theoretical factor = 0)
Image: Wikimedia Commons, Author: LHcheM
2. Atom Economy: Synthetic methods should be designed to maximize the
incorporation of all materials used in the process into the final product
• Ideally all atoms from the reagents are incorporated into a final product.
• High atom economy ↔ less waste production
• There are no co-products or byproducts in the reaction.
• The molecular waste is therefore reduced.
Relative molecular mass of the desired product

% Atom Economy = x 100
Relative molecular mass of all reactants
74 103 98 137 g/mol
275
% Atom Economy = (137/275) x 100 = 50%

Ref. The Atom Economy-A Search for Synthetic Efficiency; Barry M. Trost; Science 1991, (254), pp 1471-1477.
ATOMIC ECONOMY
▪ Traditionally, chemists are taught to maximize the yield of a reaction?

▪ Comparing the efficiencies between different reactions?
i) ii)
FW
Practice:
Route i) 1kg benzene (12.8 mole) → gave 0.82 kg product (8.4 mole) → yield = 8.4/12.8*100% = 65%
→ practical atom economy of 44.1 x 65% = 28.7% for benzene route
Route ii) 1kg butene (17.9 mole) → gave 0.96 kg product (9.8 mole) → yield = 9.8/17.9*100% = 55%
→ practical atom economy of 35.6% for butene.
▪ Planning stage, the chosen strategy that produce a greater weight of products per unit weight of reactants

Example of atom economy
Calculate atom economy of these reactions (main product was indicated with bold letters)
1) C2H2 + HCl → CH2=CHCl

2) ClCH2CH2Cl → CH2=CHCl + HCl
3) Ca(CH3COO)2→ CaO + CO2 + (CH3)2CO

4) (CH3)2CO + 2C6H5OH → (CH3)2C(C6H4OH)2 + H2O (Bisphenol A)
5) CO2 + 4H2 → CH4 + 2H2O (CO2 methanation)
6) CO2 + 3H2 → CH3OH + H2O (CO2 hydrogenation to methanol)
7) CH2=CH−CH=CH2 + 2 CO + 2 H2O → HO2C(CH2)4CO2H (Adipic acid)
8) C6H10 + 4H2O2 → C6H10O4 + 4H2O (green route for Adipic acid synthesis from cyclohexene)
9) 2C6H5Cl + Cl3C-CHO → C14H9Cl5 + H2O (pesticide DDT, forbidden to use)
10) Synthesis of aspirin

(acetylsalicyclic acid)

Effective Mass yield (EMY)
Benign: pleasant and kind;
not harmful or severe
EMY measures the environmental acceptability of a process. It is defined as the percentage of

the mass of the desired product relative to mass of all non-benign materials used in its
synthesis.
7.8 g 19.2 g 8.82 g

If we consider benzene is harmful, what is the EMY of this reaction?
EMY = 8.82/7.8 x 100 = 113%
Defining ‘non-benign’ is difficult in practice when working with complex reagents and reactants
that have limited environmental or occupational toxicity information

Carbon efficiency (CE) Reaction mass efficiency (RME)
CE is defined as the percentage of carbon in RME is the percentage of the mass of the reactants that
the reactants that remain in the final product. remain in the product
For a generic reaction A + B → C
Note: For all calculation, the reaction needs to

be balanced with stoichiometry of reactants
C4H6O4 118 C2H6O2 62

Cu
4H2 2CH3OH
Dimethyl oxalate (DMO) Ethylene glycol And other by-products

(EG)
0.5 mol (59 g) 5 mol H2 (10g) 0.40 mol (24.8 g)
0.4 x 2
Carbon efficiency (%) = x 100 = 40%
0.5 x 4
24.8
Reaction mass efficiency (%) = x 100 = 35.9%
59 + 10
3. Less Hazardous Chemical Synthesis:
Wherever practicable, synthetic methods should be designed to use and
generate substances that possess little or no toxicity to people or the
environment.
▪ Chemists use toxic substances all the time because reactive chemicals afford reactions that are kinetically
and thermodynamically favorable
▪ And unless—and until—replacement chemicals along with new synthetic protocols are developed,
inherently toxic materials will continue to be used
▪ It’s not that adhering to this principle is particularly difficult to do; it’s more that chemists are disinterested in
doing it.
Production of Na2CO3
▪ A significant reduction in life expectancy for those living in South
Lancashire, UK due to the release of HCl and CO in the air
▪ CaS caused problem for the soil
▪ This process was finally replaced by Solvay process
Contributed by David J. C. Constable, Ph.D., Director, ACS Green Chemistry Institute

Less Hazardous Chemical Synthesis
Case study: Paper Bleaching

Conventional paper bleaching with Chlorine dioxide
(ClO2):
• Produces unacceptable quantities of chlorinated
pollutants.
• Many of these pollutants are exceptionally toxic.
Alternative technology for paper bleaching with

TAML/H2O2:
• Alternative catalytic breakdown of H2O2 provides
the oxidative equivalent.
• Lower temperature and time requirements.
Source: Center for Green Chemistry and Green Engineering at Yale Image: Wikimedia Commons, Author: Sammutawe
4. Design Safer Chemicals:
Chemical products should be designed to effect their desired
function while minimizing their toxicity
Case study: Antifoulants
the hull of a ship

Conventional use of organotin compounds as
antifoulants:
• TBTO and other organotin antifoulants have long half-lives
in the environment (the half-life of TBTO in seawater is
over 6 months).
• They bioconcentrate in marine organisms (the
concentration of TBTO in marine organisms has been
found to be up to 104 times greater than in the
surrounding water). tributyltin oxide (TBTO)
• Organotin compounds are chronically toxic to marine life
and can enter food chain.
• They are bioaccumulative. https://www.scranton.edu/faculty/cannm/green-
chemistry/english/environmentalmodule.shtml

4. Design Safer Chemicals:
Chemical products should be designed to effect their desired
function while minimizing their toxicity
Case study: Antifoulants Coated with DCOI Not Coated with DCOI
Alternative 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 detaches itself and searches for a more hospitable
surface to grow upon.
• 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).

5. Safer solvents auxiliaries: The use of auxiliary substances (e.g.
solvents or separation agents) should be made unnecessary
whenever possible and innocuous when used.
(not harmful)
▪ Solvents and mass separation agents → not to mention the chemical process.
▪ Without solvents, many reactions will not proceed.
▪ Solvents → 50-80% of the mass in a standard batch chemical operation.
▪ Solvents → 75% of the accumulative life cycle environment impacts.
▪ Solvents are alternately heated, distilled, cooled, pumped, mixed, distilled under vacuum, filtered, etc.
▪ The object is to choose solvents that make sense chemically, reduce the energy requirements, have the
least toxicity, have the fewest life cycle environmental impacts and don't have major safety impacts.
Dr. Concepcíon (Conchita) Jiménez-González, Director, Operational Sustainability, GlaxoSmithKline

Example of principle #5

Case study: Sildenafil citrate production
Sildenafil citrate, commonly known as Viagra, is a selective inhibitor of phosphodiesterase 5 (PDE5). This
new drug immediately became a major seller, achieving sales of more than $1 billion during its first year on the
market. With such a rapid sales take off it was critical that the environmental performance of the synthesis was
good from the outset.
The amount of organic

Conventional sildenafil citrate synthesis included:
waste produced by the
• 11 step synthesis, which gave a 4.2% overall yield. sildenafil citrate
processes at various
• Tin chloride, a heavy metal and a major time points
environmental polluter.
• The use of stoichiometric quantities of thionyl
chloride in a solvent. This has a high environmental
impact.
• Hydrogen peroxide, which causes burns upon skin
contact and is a fire and transportation hazard,
especially when in contact with organic materials.
Dunn, P.J et al Green Chem., 2004, 6, 43-48
• Produced over 1300 L of waste per 1 kg of product.
6. 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.
▪ One of “forgotten principles” in green chemistry and engineering
▪ The chemist just follows a protocol to get a reaction to go to completion and to separate the desired product
at as high a yield as possible (?)
▪ Energy gets from chemists is devoted to heating, cooling, separations, electrochemistry, pumping and
reluctantly, to calculations related to thermodynamics (e.g., Gibbs Free Energy).
▪ Energy is a key issue for the 21st century
▪ Energy—like thinking about how to arrange a synthesis to have the fewest number of steps, or use the
lowest cost starting materials or any other aspect of interest to the synthetic or process chemist—is just
another design parameter.
Fun fact: In the lab, energy consumption: A hot plate → as a TV; a vacuum pump → 3 TVs
→ If avoiding solvent removal (as principle #5) → save energy and hence money
By Dr. David Constable, Director, ACS Green Chemistry Institute®

Case Study: Atorvastatin
Atorvastatin, a cholesterol-lowering drug, suffers from an energy-

demanding synthesis as a result of two cryogenic reactions at - 70 oC.
New biocatalytic synthesis uses enzyme DERA and shortens the
process by removing two energy intensive chemical steps.

7. Use of Renewable Feedstocks:
A raw material or feedstock should be renewable rather
than depleting whenever technically and economically
practicable.
Renewable feedstocks are often made from
agricultural products or are the wastes of other
processes; depleting feedstocks are made from fossil
fuels (petroleum, natural gas, or coal) or are mined
▪ Nature produces about 170 billion tons of plant biomass annually → we use about 3.5%
▪ Estimating that 40 billion tons of biomass → enough to completely generate a bio-based economy
▪ Technical challenge
▪ The difference between C(in) from the air, and C(out) from the energy used, is the carbon footprint ΔC
▪ In the past 10 years, significant advances have been made in the development of fuels, chemicals and
materials from renewable feedstocks
▪ Biodiesel from plant oils and algae, bioethanol and butanol from sugars and lignocellulose; platics, foams
from lignin
Vision for Bioenergy and Biobased Products in the United States https://www1.eere.energy.gov/bioenergy/pdfs/final_2006_vision.pdf

Principle #7
Important chemical
https://sites.duke.edu/apep/module-1-gender-matters/content/content-what-is-alcohol/
Principle #7
Important chemical
Can you list some applications of ethanol?
Principle #7
Important chemical
Can you list two reactions that produce ethanol?

Which one is the most common process to produce
ethanol in industry?
Non renewable
feedstocks because
acetylene is derived
from fossil fuels
Biomass, a
renewable
source
8. Reduce Derivatives:
Unnecessary derivatization (use of blocking groups, protection/de-protection, and
temporary modification of physical/chemical processes) should be minimized or
avoided if possible, because such steps require additional reagents and can generate
waste

Synthesis of 6-aminopenicillanic acid – core moiety of penicillin
Conventional synthesis of 6-aminopenicillanic acid using 3 steps and intermediate

products:
Alternative synthesis using enzyme and fewer derivatives:

9.Catalysis:
Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.
Catalysts are used in small amounts and can carry out a single reaction many times. They are
preferable to stoichiometric reagents, which are used in excess and work only once
No catalyst → almost no reaction

H3PO4/SiO2
Adsorption Reaction Desorption

https://greenchemuoft.wordpress.com/2017/07/24/greenchemprinciple9/
▪ Catalyst: a substance that changes the velocity of a reaction without itself being changed in the process
▪ Catalytic hydrogenations are widely applied in petrochemical industry
▪ Catalysis has been widely applied in the pharmaceutical and fine chemical industries
▪ Heterogeneous, homogeneous, organocatalysts, and enzymes
Contributed by Roger A. Sheldon, Ph.D., Emeritus Professor of Biocatalysis and Organic Chemistry, Delft University of Technology
(4x120 38 4x18) 4x122
(1) No catalyst
=488/590*100 = 83% atom economy 1-Phenylethanol

(product)
120 2 122
(2) With catalyst
=122/(120+2)*100 = 100% atom economy
Contributed by Roger A. Sheldon, Ph.D., Emeritus Professor of Biocatalysis and Organic Chemistry, Delft University of Technology
Case study: TAML catalyst Tetra-amido macrocyclic ligand
Degradable catalysts Elimination of chlorinated

organic substances
Decrease in energy
requirements
Further reading an article about Fe-TAML catalysts for Cleanup

10. Design for Degradation:
Chemical products should be designed so that at the end of their function they break
down into innocuous degradation products and do not persist in the environment
▪ Design of products that degrade after their commercial function in order to reduce risk or the probability of
harm occurring
▪ Biodegradation, hydrolysis, and photolysis can be designed into chemical products.
▪ In the early 1960’s, industry transitioned from non-biodegradable branched surfactants, which caused
extensive foaming and other health problems in surface waters receiving WWTP effluent, to
biodegradable linear alkyl benzene sulfonate- based detergents – an approach to innovative design that
continues today.
Contributed by Rich Williams, Founder and President at Environmental Science & Green Chemistry Consulting, LLC
DESIGN FOR DEGRADATION
BASF developed a compostable polyester film called "Ecoflex®." They are making and
marketing fully biodegradable bags, "Ecovio®,"made of this film along with cassava
starch and calcium carbonate.
Sodium dodecylbenzenesulfonate
LAS: Linear alkylbenzene sulfonates → Common detergent
▪ Alkylbenzene sulfonates 1950s-early 1960s →

Non-biodegradable Biodegradable
foam in sewage plants, rivers, and streams
Degradation and Surfactants
No more product like DDT (!)

11. 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.
Include in-process real-time monitoring and control during syntheses to minimize or
eliminate the formation of byproducts
Knowing when your product

is “done” can save a lot of
waste, time, and energy.
Analytical chemistry has been at the heart

of the environmental movement since its
inception. It’s been used in:
Industry
▪ Temp • Identification
▪ Pressure • Monitoring
▪ pH
▪ Sensor (toxic gas) • Measurement
• Characterization
Contributed by Douglas Raynie, Assistant Professor, Chemistry & Biochemistry, South Dakota State University
12. Inherently Safer Chemistry for Accident Prevention:
Substances and the form of a substance used in a chemical process should be
chosen to minimize the potential for chemical accidents, including releases,
explosions, and fires.
▪ Safety can be defined as the control of recognized hazards
to achieve an acceptable level of risk.

Eliminates the
Green exposure before ▪ Principle # 12 is known as the “Safety Principle”.
Chemistry it can happen
Elimination/
Substitution ▪ It is practically impossible to achieve the goals of Principle
Requires a 12 without the implementation of at least one of the others.
Engineering physical change
Controls to the work place ▪ Materials and processes that are safer for the environment
Requires worker also are likely to be safer for the general public.
Administrative & Work or employer to
Practice Controls DO something ▪ The manufacturing or laboratory worker is often the first in-
Requires
worker or line person to benefit from hazard reductions.
Personal Protective employer to
WEAR ▪ The graphic (adapted from OSHA) shows that the most
Equipment
something
effective means of increasing safety is eliminating the
hazard component.
RISK = (function) HAZARD x EXPOSURE

➢ Leakages
Chemical accidents include: ➢ Explosions
➢ Fires
Minimize the use of volatile liquids or gases which are associated
with the majority of chemical accidents
If possible, allow reactions to proceed under mild conditions, e.g.
ambient T & P

▪ Bhopal disaster
(carbaryl)
The flare tower where toxic methyl isocyanate

gas was released into the air.
Tank E610 contained 42 tons of liquid MIC

at the moment when the accident
happened
▪ False prediction of pressure due to a lack of online analysis
▪ Cooling system
▪ A flare tower to burn MIC gas when it escaped → disconnected
▪ A vent gas scrubber → deactivated
Case study: Production of gasoline alkylate with AlkyClean® Technology

In 2016 Albemarle and CB&I won the EPA green chemistry award for their inherently safer
AlkyClean® process technology.
AlkyClean® Technology:
• The AlkyClean® solid acid alkylation process
Conventional alkylate production: produces high quality alkylate without using
• Alkylate is typically produced from the reaction of liquid acid catalysts.
isobutane and light olefins. • The solid acid alkylation process is safer for
• This requires the use of liquid acid catalyzed both people working directly in production and
processes, such as hydrofluoric acid. for people in the area surrounding the
• Hydrofluoric acid is extremely toxic. When released it production facility.
forms clouds that can be lethal for up to five miles. • There are also environmental and economic
benefits since neither acid-soluble oils nor
spent acids are produced.
MORE EXAMPLES AVAILABLE
Presidential Green Chemistry Challenge Winners

https://www.epa.gov/greenchemistry/presidential-green-
chemistry-challenge-winners
How Industrial Applications in Green Chemistry Are Changing

Our World (white paper) by American Chemical Society

SYNTHESIS COMPARISON EXERCISE

Dihydropyrimidone is a
pharmaceutical compound
that displays medicinal
properties as vasodilatory
calcium-channel blockers
and anti-viral, anti-
bacterial, and anti-
inflammatory agents. More
than one synthetic
schemes have been
proposed for its synthesis
since the late 1800s.
Compare the two synthetic
routes and analyze which
pathway is greener. In your
argument, be sure to
consider and compare all
aspects of the reaction.

SUMMARY
• P – Prevent wastes
• R – Renewable materials
• O – Omit derivatization steps
• D – Degradable chemical products
• U – Use safe synthetic methods
• C – Catalytic reagents
• T – Temperature, pressure ambient
• I – In-process monitoring
• V – Very few auxiliary substances
• E – E-factor, maximize feed in product
• L – Low toxicity of chemical products
• Y – Yes, it is safe
Productively !!!
(Samantha Tang, Richard Smith and Martyn Poliakoff )

Check point
Example: Taking the simple esterification of butanol with acetic acid, the balanced equation for
the reaction is:
FW 74 60 116
A standard procedure is to mix butanol (37 g) with glacial acetic acid (60 g), and a small amount
of sulfuric acid catalyst (ignored in all calculations). Following completion of the reaction the
mixture is added to water (250 g). The crude ester is washed further with water (100 g), then
saturated sodium bicarbonate solution (25 g) and finally water (25 g). After drying over 5 g of
anhydrous sodium sulfate the crude ester is distilled to give product (40 g). Considering that
butanol is nonbenign material.
Calculate: Reaction yield? Atomic economy?

E-factor? (considering that water is also a part of waste)
Effective Mass Yield (EMY)?
Reaction mass yield (RMY)?


Green Chem - Week 1-4 - Full-2023!09!20-Lecture (Student)

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Green Chemistry

Dr. Nguyễn Đăng Khoaa, Dr. Lê Vũ Hàa, Dr. Hồ Hoàng Phướcb

Objectives of the course

Content of the course

2023-08-25 Chalmers University of Technology 2

- To understand the current role of chemical industry in

- Present principles of green chemistry

- Apply the green-chemistry principles to improve simple

2023-08-25 Chalmers University of Technology 4

2023-08-25 Chalmers University of Technology 5

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Overview modern chemistry

Impact of chemical industry to environment

12 principles of Green Chemistry

Catalysis for Green Chemistry

Solvents, reactors, renewable materials

Some examples of Green Chemistry

2023-09-20 Chalmers University of Technology 7

Week 1 Introduction to Green Chemistry

Week 11 Green improvements of chemical production: Reactors

Week 14 Green improvement of industrial processes: Some examples

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2023-09-20 Chalmers University of Technology 12

▪ Transportation – production of gasoline and diesel from

2023-09-20 Chalmers University of Technology 13

✓ Health & Beauty Products

One barrel = 159 L = 42 galons

Quiz: how many refinery does Vietnam have by 2022?

a) 2000 b) 500 c) 350 d) 50

Bulk chemicals/ Fine Customers of

Naphtha, styrene Poly-

Fine chemicals > 10000 chemicals

Natural gas, Coal

2023-09-20 Chalmers University of Technology 19

Give names of 5 domestic chemical companies (in Vietnam)

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• DDT was a broad spectrum insecticide.

Colorado beetle Housefly malaria-carrying mosquitoes

DDT was used in the military to DDT aerial delivery to protect

2023-09-20 Chalmers University of Technology 25

Source: Center for Green Chemistry and Green Engineering at Yale

Which one is the most common used plastic?

Source: Center for Green Chemistry and Green Engineering at Yale

2023-09-20 Chalmers University of Technology 28

Vietnam final total energy consumption by sector in 2012

❖ Which one is the main source?

Coal, natural gas

Thermal power plant

Hoa Binh Tra Vinh Ninh Thuan

Hydropower plant Non-hydro renewables (wind, solar)

2023-09-20 Chalmers University of Technology 32

Is there any thermal power plant in your home town?

2023-09-20 Chalmers University of Technology 33

(3-17%) 98-99% cleaner

• > 60 millions motorcycles registered in Vietnam by 2019

Quiz: how many industrial parks are there in Vietnam up to 2022?

Personal Local Global

▪ Physiological ▪ Damage the natural ▪ Acid rain