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absorbents be prepared from CO2 itself, for instance, or coupled somehow to the CO2 separations? What inexpensive feedstocks can be used to make nontraditional absorbents? Predict and exploit nonideal absorption For thermodynamically driven separations, the equilibrium between gas and liquid phases, as embodied in absorption isotherms, ultimately determines the effectiveness of a material for a separation. To achieve energy-efficient separations, control over chemistry must be accompanied by control over isotherms. These isotherms are determined both by the enthalpy Carbonic Anhydrase: Biomolecules that Reversibly Catalyze CO2 Hydration Carbonic anhydrases are enzymes that catalyze the hydration of carbon dioxide and the dehydration of bicarbonate: – CO+HO⇄HCO +H This reversible reaction can be exploited to separate CO2 from other gases. These carbonic anhydrase-driven reactions are of great importance in a number of human tissues, where they are important in facilitating diffusion and transport of CO2, secretion of bicarbonate and protons, and maintaining acid–base and fluid balance. In particular, carbon dioxide generated by metabolism in all cells diffuses to red cells in the blood, where carbonic anhydrase catalyzes the formation of bicarbonate for transport to the lungs. In the lungs, carbonic anhydrase catalyzes the formation of carbon dioxide for exhalation. 223 Carbonic anhydrases in humans consist of a single polypeptide chain with a zinc atom complexed by three histine ligands. These enzymes are among the fastest catalysts known; at low concentrations of CO2 and HCO3 , the reaction is limited by diffusion; and–at high concentrations, the turnover rate is 106 reactions per second per mole enzyme. Catalysis of this reaction is reversible. CO2 hydration is catalyzed by the enzyme-bound zinc-hydroxide, whereas bicarbonate reacts with the zinc-water form of the enzyme (pKa ~ 7). + Closeup of active site of carbonic anhydrase isozyme IIshowing three histidine residues and hydroxide coordinating zinc. Image courtesy of Wikimedia Commons. and the entropy ∆S ̊ of absorption, through ∆G ̊(T) = ∆H ̊(T) – T∆S ̊(T) (e.g., if the absorbent reacts with the gas ln Keq = –∆G ̊/RT, where Keq is the equilibrium constant). In an ideal absorption system, the enthalpy of absorption is independent of the amount of absorbed material. Ideality gives the familiar Henry’s Law behavior for physical absorption 48PDF Image | 2020 Carbon Capture
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