CHEM0077/8/9 Topics in Modern Chemistry

or
CHEM0067: Advanced Topics in Energy and Environmental Science

Topic E1: Green Chemistry, Renewable Energy

Landscape and the Role of Nanomaterials

Prof Jawwad A. Darr

Topic E1: J.A.Darr

Handout 1: Introduction to Green Chemistry and Sustainable Development

Contents: • Sustainable development •

Principles of green chemistry • Life cycle
analysis • Waste management • E-factor

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 Population Pressures

• 20th century – 1.6 – 6 billion

• saw +60% life expectancy
• Emerging nations want good standards
• Chemicals/Genetics-high crop yields.
• Demands are set to grow
• Increase in EPA legislation

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 The Costs of Waste

• Compliance costs
• 10 billion Euro in EU, USA each.
• Govts are increasing costs for waste
• Try to encourage recycling, waste min.
• Can be up to 40% cost of production

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 Other Costs

• Inefficient manufacturing, by-products

• Extra energy (more molecules)
• Poor public relations – consumer conscience
• Worker Morale
• Financial costs are still major driver

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 Sustainable Development

Development which meets the needs of the

present without compromising the ability of the
future generations to meet their own needs” [1]

[1] 1987 UN Commission on Environment and Development.[aka Bruntland]

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Topic E1: J.A.Darr
Green Chem., 2005,7, 761-762
 Life Cycle Assessment:

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IMAGE: https://www.innovationservices.philips.com/news/life-cycle-assessment-finding-best-approach-company/
 Life Cycle Assessment:

• We can look at the amount of energy input, consumables input and waste
generated for each step of a products so called life.
• This is viewed as a life cycle assessment which breaks up the various
stages from raw materials to ‘end of life’.
• This shows us that the end of life part is particularly important.

Remember though green chemistry is about waste reduction at source not

recycling, but this can’t be ignored. We can no longer afford to use single use
products. Pollution prevention can be considered at every stage

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 LCA and Sustainable Development

• Min E and Materials in

• Utilised to max efficiency
• Max use of renewable resources.
• Recyclability.
• Extend durability/performance
• Economic benefit for producer.
• Release of harmfuls removed/minimised.

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 Other costs

Figure: Stages of a product life cycle (From Green Products by Design: Choices for a Cle aner Environment. U.S. Congress,
Office of Technology Assessment, OTA-E-541).

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Think about it now! Will be addressed in next Synchronous content !

Management Options

PUT THESE IN ORDER 6 = Most desirable and 1= least desirable

1.New /cleaner technology or Retrofitting
2.Dispose to landfill
3.Recycling (on site or off site)
4.Product changes (prevent)
5.Process changes (feedstock, etc.)
6.Waste reduction at source (prevent)

Topic E1: J.A.Darr

 Recipe for 20th Century

• Organic solvent,
• Dissolve reagent,
• Reaction, repeat to get product,
• Discard waste, recover solvent,
• Transport products,
• Release product into ecosystem
with no evaluation.

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 Recipe for 21st Century

• Design molecule for min. env. impact

• Manufacture from renewable feedstock
• Use a long-life catalyst
• Solvent-less or recyclable solvent
• Least steps
• Manufacture close to use

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 Efficiency of a Reaction

Yield, selectivity – do not give an idea about waste prod.

Atom economy – atoms converted to useful product.
A + B -----> C + D + E
Thermodynamic efficiency.

Notes: Yield and selectivity are traditional methods for defining efficiency, e.g. you can get 100%
yield and purity but still get MORE WASTE THAN PRODUCT!! However, the amount of atoms
converted to useful product and how many to waste is a better measure. Atom economy is a
quantitative measure of this. Thermodynamic efficiency is another measure of considering
energy efficiency via ‘lost work’ - done by calculating the theoretical work potential of the raw
materials and of the final product. Hence thermodynamic efficiency can be calculated.

Topic E1: J.A.Darr

 Worked example to follow in next Synchronous content !

E-Factor

• E-Factor [Coined by Sheldon (1994).]

• Also, do the calculation w/wo water as waste (recycling water).

E factor =
kg waste / kg product

The E Factor: fifteen years on. Roger A. Sheldon Green Chem.,

2007,9, 1273-1283

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 Answers to follow in next Synchronous content !

E-Factor

Reorder these
Two columns

The E Factor: fifteen years on. Roger A.

Sheldon Green Chem., 2007,9, 1273-1283
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 Atom Economy

(Total mass of useful product atoms /

Total mass of product atoms)(x100)

CaCO3 => CaO +CO2

100 56 44
AE = 56%

Topic E1: J.A.Darr

LCA and Sustainable Development

• Min E and Materials in

• Utilised to max efficiency
• Max use of renewable resources.
• Recyclability.
• Extend durability/performance
• Economic benefit for producer.
• Release of harmfuls removed/minimised.

Topic E1: J.A.Darr

 UNSDGs

• A call for action by all countries – poor, rich and middle-income

• Promote prosperity while protecting the planet.
• Ending poverty must go hand-in-hand with economic growth
• Address a range of social needs including education, health, social
protection, and job opportunities
• Also tackle climate change and environmental protection.

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Topic E1: J.A.Darr
ACTION: investigate an idea and be ready to share it as a 1 minute oratory
with the group in the next synchronous session

Closing Question

Think about an area of energy technology which involves green

chemistry or unsustainable elements

Questions
1. What is the technology?
2. What are the sustainability issues in developing nations?
3. What social issues in the context of UNSDGs that are
relevant to your answer for Q1 and Q2 ?

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ACTION: investigate an idea and be ready to share it as a 1 minute oratory
with the group in the next synchronous session

Example Answer from Closing Question

• The development of better batteries using alternatives to Li

(Na ion and other, based on non lead).

• This offers a route to low cost batteries for grid and

automotive energy storage.

• The availability of clean non-polluting transport is vital for the

UNSDG 11 and 8.

• Also, the availability of lights at night from batteries allows

people to access education and reading, so this affects
gender equality and education (UNSDG 4 and 5)

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Appendix:

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 Appendix: LCA
• Typically, a product life cycle is a linear progression:
• First, raw materials are extracted from the earth.
• Second, raw materials are processed into finished materials. For
example, bauxite ore into Al and oil into plastics.
• Third, materials are manufactured or assembled into a final
product. This stage can be in two parts: e.g. car parts then car
• Fourth is the use stage when a consumer has control of the product.
• Finally is the waste management stage or end-of-life stage when the
product is broken down into component materials for remanufacturing
or recycling, or landfill
• Also sixth stage of materials and product transport between stages
• During each of these stages, the activities that occur require material
and energy resources, and generate wastes and emissions. Material
and energy resources include items such as ores, catalysts, water,
coal, natural gas, or electricity. Wastes include solid wastes (trash) or
hazardous wastes. Emissions include pollutants released to the air,
such as sulfur dioxide or carbon dioxide or soot, or to the water, such
as sewage or solids.
• Life cycle assessment gathers information about the quantity of these
resources and wastes at each life cycle stage.
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 Mobile Phone
Extraction
• A cell phone is made up of many materials. In general, the
handset consists of 40 percent metals, 40 percent plastics, and
20 percent ceramics and trace materials.

The Nine Lives of a Cell

Cell phones consist of nine basic parts, each of which has its own
life cycle: Circuit board/printed wiring board, Liquid crystal display
(LCD), Battery, Antenna, Keypad, Microphone, Speaker, Plastic
casing, Accessories (such as adapters, headsets, carrying cases,
and decorative face plates)

See document on The Life

Cycle of a Cell Phone

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(Taken from http://ourmobilegeneration.org/goals/1-sustainable-smartphone/phases/21-inspiration/inspirations/11)

Topic E1: J.A.Darr

 Appendix: Recommended reading
1. The E Factor: fifteen years on. Roger A. Sheldon Green Chem., 2007,9, 1273-1283

2. https://www.acs.org/content/acs/en/greenchemistry/principles/12-principles-of-green-
chemistry.html

3. https://www.sigmaaldrich.com/chemistry/greener-alternatives/green-chemistry.html

4. Green Chemistry: Science and Politics of Change, Green Chem 2008

http://www.precaution.org/lib/green_chemistry.020802.pdf

5. PRODUCTIVELY green principles by Poliakoff, Green Chem., 2005,7, 761-762

6. The 24 Principles of Green Engineering and Green Chemistry: “IMPROVEMENTS

PRODUCTIVELY
”http://www.scheikundeinbedrijf.nl/content/Modules/Modulenaam/Files/b719469m.pdf

7. Life-cycle engineering (LCE) can be defined as “sustainability-oriented product development

activities within the scope of one to several product life cycles.” see self study video
https://www.youtube.com/watch?v=Ub2TLg03IlU

8. https://www.un.org/sustainabledevelopment/sustainable-development-goals/

Topic E1: J.A.Darr

 CHEM0077/8/9 Topics in Modern Chemistry
or
CHEM0067: Advanced Topics in Energy and Environmental Science

Topic E1: Green Chemistry, Renewable Energy

Landscape and Nano

Prof Jawwad A. Darr

Topic E1: J.A.Darr

 Topic E1: J.A.Darr

Green Chem., 2005,7, 761-762

 Handout 2: Risk and Hazard

Contents: • Risk and Hazard •

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 Reduction of Risk & Hazard
HAZARD x ACTION RISK

Safer processes by design – making things fool proof!

• HAZARD is the potential to cause harm;

• RISK on the other hand is the likelihood of harm (in defined

circumstances, and usually qualified by some statement of the
severity of the harm)

The relationship between hazard and risk must be treated very

cautiously. If all other factors are equal - especially the
exposures and the people subject to them, then the risk is
proportional to the hazard. However all other factors are very
rarely equal.
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 Reduction of Risk & Hazard

Which of these materials is likely to cause harm?

1. Potassium Dichromate is a highly toxic carcinogenic

chemical used in breath tests….. Discus.

2. Flour would not be considered by many to be a hazardous

substance. ….. Discuss.

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 Reduction of Risk & Hazard
Which of these materials is likely to cause harm?

1. Potassium Dichromate is a highly toxic carcinogenic chemical.

It is used in some techniques to analyse exhaled breath for alcohol content.

However, for this purpose it is sealed in a tube, and does not become airborne
when air is drawn over it. Therefore, although it is a highly hazardous
substance, its use as described, does not present any risk to the subject.

2. Flour would not be considered by many to be a hazardous substance.

A jar of it on a shelf would not have a skull and crossbones
depicted on it together with other hazard warnings, as
might have been the case for a bottle of potassium
dichromate However, if a baker was exposed over a period
of time to airborne flour dust and/or dust by skin contact,
he/she could develop dermatitis (an inflammation of the
skin), conjunctivitis (inflammation of the eyes), rhinitis
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 Reduction of Risk & Hazard

Safe Design
• Disasters; Bhopal (’84) 20 k dead?
• Insecticide called cararyl (MIC, Phos.)
• Simple but deadly chemistry
• It is easy to blame human error

Methylamine (1) reacts with

phosgene (2) producing methyl
isocyanate (3) which reacts with 1- Topic E1: J.A.Darr
naphthol (4) to yield carbaryl (5)
 Reduction of Risk & Hazard

Safe Inherently Safe Design

• Best to eliminate the hazard

• Risk = hazard x exposure

• “What you don’t have can’t hurt you”

• Make on site and J-I-T

• Avoid hazardous chemicals !

Topic E1: J.A.Darr

 Reduction of Risk & Hazard
Common Solvents
• Organic solvents are widespread.
• Air/water pollution
• Toxic, carcinogenic
• Alternatives to organic Solvents
• Best not to use any solvent at all !!!

This is not a new concept

‘In an ideal chemical factory there is, strictly
speaking, no waste but only product. The better a
real factory makes use of its waste, the closer it
gets to its ideal, the bigger is the profit’

R. W. Hoffmann (1848)

Topic E1: J.A.Darr

 Green Challenges with Materials

• Inorganic materials are important in a range of important

devices and technologies which help meet our future energy
demands [energy harvesting conversion and storage devices]

The key challenges are to do with Sustainability

This generally means…

1.Scarcity /abundance
2.Cost and price stability
3.Security of supply and
4.Environmental / toxicity impact or
considerations [life cycle]

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 Green Challenges with Materials

Abundance (atom fraction)

of the chemical elements in
Earth's upper continental
crust as a function of
atomic number. The rarest
elements in the crust
(shown in yellow) are the
most dense.

In order to meet the future demands for energy, and meet our storage needs, a
number of inorganic materials device technologies will be critical;
Solar cells (e.g. Dye Sensitised) and transparent
conducting oxides, Lithium ion batteries and
supercapacitors, Solid oxide fuel cells
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Topic E1: J.A.Darr
 Transparent Conducting Oxides

• combination of high electrical

conductivity and optical transparency
for flat panel displays, solar cells and
other opto-electronics

• ITO doped with SnO2 of 10 wt.% in

In2O3 commercialized. ITO film
electrical conductivity of ~10-4 Ω·cm
and high transmittance of ~90% (on
glass.)
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 Transparent Conducting Oxides

• Disadvantages; high cost, instability, poor surface roughness, and

toxicity. e.g. amorphous ITO film deposited at low temperature have
low resistance under moist heat, which leads to a decrease in
conductivity and light transmittance.
• Price of Indium is increasing due to current scarcity of Indium sources.

• However, some zinc-based TCO materials are

comparable to the ITO films, as well as low
cost, high stability, excellent surface uniformity,
and good etching selectivity.
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 Topic E1: J.A.Darr
https://cff2.earth.com/uploads/2019/01/22203357/elements.png
Image from http://metalpedia.asianmetal.com/metal/rare_earth/application.shtml

Topic E1: J.A.Darr

The Importance of Materials in “Energy” Devices

• In each of these devices a number of inorganic

materials and / or organometallics are critical to the
performance of these devices, affecting their ability
to store or transfer energy. Ultimately a number of
things will determine choices and performance;.

• the method of synthesis and the material in question

 Particle size, surface area, porosity, particle coatings

 The crystal structure /phase, bandgap etc.
 Life cycle (including recyclability and lifetime), E-
factors, sustainability considerations, Safety / toxicity
considerations, cost/availability
 Socioeconomic factors
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 Appendix: Recommended reading

1. Rare Earth Elements: Industrial Applications and Economic Dependency

of Europe Procedia Economics and Finance Volume 24, 2015, Pages
126-135, https://doi.org/10.1016/S2212-5671(15)00630-9

2. Elements used to make smartphones and devices are becoming scarce;

https://www.earth.com/news/elements-smartphones-scarce/

3. Elements of Scarcity, David J. Cole-Hamilton, Chemistry International |

Volume 41: Issue 4. DOI: https://doi.org/10.1515/ci-2019-0409 |
Published online: 31 Oct 2019 (pdf is on Moodle)

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 Appendix: Recommended reading
http://metalpedia.asianmetal.com/metal/rare_earth/application.shtml

Topic E1: J.A.Darr