12ChF322 Green Chemistry

Green Chemistry
Candidates should be able to: (a) describe principles of chemical sustainability: (i) using industrial processes that reduce or eliminate hazardous chemicals and which involve the use of fewer chemicals, (ii) designing processes with a high atom economy that minimise the production of waste materials, (iii) using renewable resources such as plant-based substances, (iv) seeking alternative energy sources such as solar energy, rather than consuming finite resources such as fossil fuels that will eventually be exhausted, (v) ensuring that any waste products produced are non-toxic, and can be recycled or biodegraded by being broken down into harmless substances in the environment; (b) explain that the apparent benefits may be offset by unexpected and detrimental side effects; (c) explain the importance of establishing international cooperation to promote the reduction of pollution levels; (d) discuss issues of sustainability in contexts based on the principles in ac;

Green chemistry is not, primarily, about using plants or bacteria to do chemistry rather than traditional chemical substances, although this is a common misconception. The aim is to manufacture chemical products SUSTAINABLY. " BENIGN BY DESIGN" - so that we can do so in the long term without harming the planet - so that we can do so without running out of finite resources (using renewables) We can break this down into a series of OBJECTIVES for better industrial processes: reduce or eliminate production of, and use of, hazardous chemicals ensure that any waste products produced are non-toxic, and can be recycled or biodegraded use renewable resources e.g. plant-based substances minimize energy requirements (by using catalysts and using sustainable energy sources) design processes to achieve high atom economy and thereby minimise waste materials waste costs money ! (disposal, handling etc.) You will be expected to be able to EVALUATE a given reaction to give an opinion about its "green-ness". Considering %yield and Atom Economy: high %yield means very efficient conversion from reactants to products increasing %yield means reducing waste of starting materials increasing Atom Economy means reducing the amount of waste products Considering use of catalysts: Catalysts can make chemical companies' processes more sustainable because: catalyst is not used up in reaction (may be used in one step, regenerated in subsequent step)

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12ChF322 Green Chemistry reactions take place at lower temperatures reactions require lower EA so use less fuel, and reduce energy cost less CO2 emitted into atmosphere, and fossil fuel reserves last longer different reactions may be possible with less waste or better atom economy reactions using less hazardous chemicals may be possible catalysts or enzymes can generate specific products

Example of a process which is NOT green ! Consider the laboratory method for oxidizing an alcohol to make a carboxylic acid: - we dissolve potassium dichromate (carcinogenic) in conc sulphuric acid (hazardous) - we add this to the alcohol and warm it if needed - we reflux the mixture (using heat from burning a fossil fuel, natural gas) - we distill the carboxylic acid (using more heat energy) - we throw away all the unreacted alcohol, the remaining acid, the green chromium(III) ion solution (v. toxic) so low atom economy. How would we do it better ? - replace the heating with solar heating / use a catalyst to speed up reaction ? - find an oxidizing agent which is less hazardous ? - use an oxidizing agent which dissolves in the alcohol rather than having to be dissolved in a solvent which is later wasted ? - look for a biological route (e.g. enzyme) for converting alcohol to carboxylic acids ? Examples of new greener industrial processes over the past few decades: New foams such as Pyrocool FEF have been invented to put out fires effectively without producing the toxic or ozone-depleting waste products found in other halogenated fire-fighting materials. Lead has largely been eliminated from use in petrol (leaded/unleaded old engines) Solvent-free reactions, ie use of reagent as solvent or use of 'supercritical' CO2 For dry cleaning, liquid supercritical CO2 can be used as a safer solvent than chlorinated hydrocarbons. Laws of unintended consequences We have to be aware that there may be effects we hadn't taken into account. When Thomas Midgeley pioneered the use of CFCs as refridgerant gases and in fire extinguishers he didn't know they would have any impact on the ozone layer. A more current example production of biodiesel uses up grain crops and land needed for food, with poorer countries being worse affected. Clearance of rainforest for additional planting of food or biofuel crops also occurs, damaging the planet's ability to remove CO2 from the atmosphere.

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