green chemistry principles

Green chemistry principles are linked to chemical engineering, focused on the design of products and processes aimed at reducing the generation of hazardous substances.

What are the principles of green chemistry?

Green chemistry graduated from a global drive to increase the awareness of chemical pollution and the Earth’s rapid resource depletion. The development of green chemistry aligned to a shift in environmental problem-solving strategies, directly linked to the mandated reduction of the planets industrial emissions. These concepts surrounding green chemistry are often referred to as clean and sustainable chemistry.

The Environmental Protection Agency (EPA), played an early pioneering role in liberating green chemistry via numerous pollution prevention programs and facilitating readily available funding. The University of York simultaneously led the way with the formation of the Green Chemistry Network within the Royal Society of Chemistry.



12 Principles of green chemistry (definition)

In 1998, Anastas and Warner published a set of 12 principles, formulating ways to reduce the environmental and health impacts of chemical manufacture and prioritise the development of green chemistry technologies.

The principles include; the optimisation of processes to maximise the raw material percentage present in the end product, the greater use of renewable material feedstocks, application of safer, environmentally benign substances, including solvents, whenever possible and the design of more energy efficient processes.

The 12 principles:

  1. Prevention. Preventing waste.
  2. Atom economy. Synthetic creation to maximise the incorporation of all materials used in the process into the final product.
  3. Less hazardous chemical syntheses. Synthetic methods should avoid using or generating environmentally toxic substances.
  4. Designing safer chemicals. Chemical products should be designed to achieve their desired function.
  5. Safer solvents and auxiliaries. Auxiliary substances should be avoided wherever possible.
  6. Design for energy efficiency. Energy requirements should be minimised (ambient temperature and pressure processes).
  7. Use of renewable feedstocks. Renewable feedstocks are preferable to non-renewable ones.
  8. Reduce derivatives. Unnecessary generation of derivatives (steps requiring additional reagents generating additional waste).
  9. Catalysis. Catalytic reagents that can be used in small quantities to repeat a reaction are superior to stoichiometric reagents.
  10. Design for degradation. Chemical products should be designed so that they do not pollute the environment.
  11. Real-time analysis for pollution prevention.
  12. Inherently safer chemistry for accident prevention. The substances in a process should be chosen to minimise risks such as explosions, fires, and accidental releases.


The future of green chemistry (examples and applications)

Green chemistry solvents

Commonly used solvents are generally toxic. Green solvents are generally less harmful to the environment. The manufacture of solvents from biomass can, in certain cases, be more harmful to the environment than creation from fossil fuels. The environmental impact of solvent manufacture must be carefully considered when it is selected for a product. If the solvent is being used and recycling is feasible, then the energy cost and environmental harm via recycling should be considered. For example, water, requires a lot of energy to purify, isn’t the greenest choice. However, a solvent contained in a consumer product is likely to be released into the environment upon use, and the impact of the solvent itself is more important than the energy cost and impact of solvent recycling. In this instance, water is the green choice. In summary, the impact of the entire lifetime of the solvent, from cradle to grave, to cradle, has to be considered.

Another example, whereby water is a sustainable choice, is in toilet cleaner. On the flip side it is not a green solvent in the production of polytetrafluoroethylene (PTFE). In the production of PTFE, there is a requirement for perfluorinated surfactants. In summary, no solvent can be declared to be a green solvent unless it is linked to a specific application.


Where is green chemistry used? – synthetic techniques

Enhanced synthetic techniques often provide improved environmental performance. Chauvin, Grubbs and Schrock, won the Nobel prize for Chemistry, for the development of the metathesis method in organic synthesis, a significant contribution to green chemistry. Developments in organic synthesis include: use of supercritical carbon dioxide, aqueous hydrogen peroxide for clean oxidations and the use of hydrogen in asymmetric synthesis.


Green pharmacy and bioengineering

Bioengineering is also seen as a future technique for leveraging green chemistry. Key process chemicals can be synthesised in engineered organisms, such as shikimate, a Tamiflu precursor which is fermented in bacteria.


Green chemistry industrial example – carbon dioxide as blowing agent

Dow Chemical won the 1996 Greener Reaction Conditions award for their 100% carbon dioxide blowing agent for polystyrene foam production. CFC’s were previously used in the production process of the foam sheets. Flammable, and toxic hydrocarbons have been used as substitutes, which have alternative negative effects. Dow Chemical discovered that supercritical carbon dioxide works equally as well as a blowing agent, allowing the polystyrene to be more easily recycled. The CO2 used in the process is recycled, so the process is net zero.


Hydrazine – a future green product

The Peroxide Process for producing hydrazine without cogenerating salt aligns to principle 2. Hydrazine is traditionally produced by the Olin Raschig process from sodium hypochlorite and ammonia. In the greener Peroxide process hydrogen peroxide is employed as the oxidant and the side product is water. It also tackles principle 4 and does not require additional extracting solvents.


Goals of green chemistry – Lactide

In 2002, Cargill Dow won the Greener Reaction Conditions Award for their improved method for polymerization of polylactic acid. Lactic acid is produced from lactide, the cyclic dimer ester of lactic acid. The L,L-lactide enantiomer is isolated by distillation and has applications including textiles and food packaging. The NatureWorks PLA process substitutes renewable materials for petroleum feedstocks, doesn’t require the use of hazardous organic solvents and results in a high-quality polymer that is recyclable.


Carpet tile backings – Ecoworx green compounds

Shaw Industries identified polyolefin resins as the base polymer of choice for EcoWorx, due to the low toxicity, superior adhesion properties and its potential for recycling. The EcoWorx compound also had to be designed to be compatible with nylon carpet fiber. Polyolefins are compatible with known nylon-6 depolymerization methods. PVC interferes with those processes.

From its inception, EcoWorx met all of the design criteria necessary to satisfy the needs of the marketplace from a performance, health, and environmental standpoint. Research indicated that separation of the fiber and backing through elutriation, grinding, and air separation proved to be the best way to recover the face and backing components, but an infrastructure for returning postconsumer EcoWorx to the elutriation process was necessary. EcoWorx is recognised by MBDC as a certified cradle-to-cradle design.



Bio-succinic acid – green renewable alternative production

Succinic acid is a platform chemical that is an important starting material in the formulations of everyday products. BioAmber developed a technology that produces succinic acid from the fermentation of renewable feedstocks at a lower cost and reduced energy expenditure, than the petroleum equivalent.

Green laboratory chemicals

The Massachusetts Institute of Technology created a Green Alternatives Wizard, to help identify alternative laboratory chemicals. Replacing toxic chemicals such as ethidium bromide, xylene, mercury, and formaldehyde were key. Over usage of solvents in chemical manufacturing led to a focus on introducing greener solvents into the earliest stage of of these processes: laboratory-scale reaction and purification methods. Globally, GSK and Pfizer have both published Solvent Selection Guides for their Drug Discovery chemists.



Catalysis and green chemistry

Research at the University of Bonn and Lehigh University have created a titanium based catalyst, providing a non-toxic equivalent to ruthenium and iridium catalysts, traditionally very expensive and toxic to the environment.

Green light leverages the catalyst, promoting electron transfer, leading to very useful organic intermediates. Radicals are liberated that initiate further reaction cycles, lending to the potential of a variety of chemical products. A photo redox catalyst depends upon the wavelength utilised for irradiation. Unlike UV light, which has a tendency to breakup the organic compounds, green light is not so aggressive but harbours enough energy to activate the reaction.



Summary of the need and benefits of green chemistry

Human wellbeing

  • Cleaner air: Less release of hazardous chemicals to air leading to less damage to lungs
  • Cleaner water: less release of hazardous chemical wastes to water leading to cleaner drinking and recreational water
  • Increased safety for workers in the chemical industry; less use of toxic materials; less personal protective equipment required; less potential for accidents (e.g., fires or explosions)
  • Safer consumer products of all types: new, safer products will become available for purchase; some products (e.g., drugs) will be made with less waste; some products (i.e., pesticides, cleaning products) will be replacements for less safe products
  • Safer food: elimination of persistent toxic chemicals that can enter the food chain; safer pesticides that are toxic only to specific pests and degrade rapidly after use
  • Less exposure to such toxic chemicals as endocrine disruptors

Nature and the environment

  • Chemicals are released through emissions during manufacturing, or by disposal and by uses directly e.g. pesticides. A global directive to drive processes to capture degradable methods and fundamental recycling at all stages of production
  • Plants and animals suffer less harm from toxic chemicals in the environment
  • A deceleration of global warming e.g. ozone
  • Reduced chemical impact on ecosystems

Global commerce and business

  • Optimised chemical reactions across production, greater percentage yield
  • Reactions requiring fewer mid steps, leading to cost savings per product
  • Reducing waste and the forms of waste e.g. eliminating toxic and hazardous waste products
  • Manufacturing carbon footprint reduction, leading to net zero products



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