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Carbon Dioxide


The use of supercritical CO₂ (carbon dioxide gas above its critical temperature, 31.1°C, and critical pressure, 73.8 bar) as a solvent has many advantages: it is non-flammable; non-toxic (although is an asphyxiant at high concentrations); readily available (it is a by-product of many processes, for example, brewing, ammonia synthesis, and combustion); can be easily recycled, and leaves no residues.[1] It is possible to tune the solvent properties simply by optimizing temperature or pressure. The use of small amounts of co-solvents (e.g., MeOH, MeCN, THF) can further modify solvent properties. High diffusion rates offer potential for increased reaction rates and scCO₂ is also inert to oxidation and resistant to reduction.

Supercritical carbon dioxide is, however, not without drawbacks—the capital cost of high-pressure equipment and energy costs for compression of carbon dioxide (particularly for large-scale work) can be disadvantageous.[2] Other potential issues include its reactivity in the presence of some nucleophiles and the fact that it is a relatively weak solvent; although as mentioned earlier, this can be modified via the use of co-solvents.

Recommended reading:

W. Leitner and P. G. Jessop, Green Solvents, Supercritical Solvents, Handbook of Green Chemistry (ed. P. T. Anastas) vol. 4, 2013.

  1. N. Tanchoux and W. Leitner, Supercritical Carbon Dioxide as an Environmentally Benign Reaction Medium for Chemical Synthesis, in Handbook of Green Chemistry and Technology, Blackwell Science Ltd, 2007, pp. 482-501.
  2. N. Winterton, Chemistry: Necessary but not Sufficient, in Chemistry for Sustainable Technologies : A Foundation, Royal Society of Chemistry, Cambridge, UK, 2011, ch. 8, pp. 194-252.