Carbon dioxide chemical synthesis

Carbon Dioxide A colorless, tasteless gas, CO2, is found in the atmosphere. It is produced as a result of metabolism (e.g., oxidation of carbohydrates) and is used by plants in photosynthesis. Carbon dioxide has low toxicity and is noncombustible. Derived industrially from synthesis gas in ammonia production and from cracking of hydrocarbons. Used widely in refrigeration, carbonated beverages, chemical synthesis, water treatment, medicine, fire extinguishing, and as inert atmosphere. 

Yong, T.-M., Hems, W.P., van Nunen, J.L.M. et al. (1997) Synthesis of fluorinated block copolymers and their application as novel polymerization surfactants in supercritical carbon dioxide. Chemical Communications, 1811-1812. 

In addition to chemical synthesis and enhanced oil recovery, gaseous carbon dioxide is used in the carbonated beverage industry. Carbon dioxide gas under pressure is introduced into mbber and plastic mixes, and on pressure release a foamed product is produced. Carbon dioxide and inert gas mixtures rich in carbon dioxide are used to purge and fiH industrial equipment to prevent the formation of explosive gas mixtures. 

Synthesis gas is a major source of hydrogen, which is used for producing ammonia. Ammonia is the host of many chemicals such as urea, ammonium nitrate, and hydrazine. Carbon dioxide, a by-product from synthesis gas, reacts with ammonia to produce urea. 

Great promise exists in the use of graphitic carbons in the electrochemical synthesis of hydrogen peroxide [reaction (15.21)] and in the electrochemical reduction of carbon dioxide to various organic products. Considering the diversity in structures and surface forms of carbonaceous materials, it is difficult to formulate generalizations as to the influence of their chemical and electron structure on the kinetics and mechanism of electrochemical reactions occurring at carbon electrodes. 

A fundamental question for all reactions which could have been involved in the early phase of chemical evolution is that of the origin of the reduction equivalents necessary for the autotrophic synthesis. For example, the synthesis of one molecule of glucose from carbon dioxide requires 24 electrons, while the synthesis of the amino acid cysteine requires as many as 26 electrons per molecule of amino acid ... 

With reference to the homogeneous catalyst systems thus far reported for the synthesis of hydrocarbons/chemicals from carbon monoxide and hydrogen, only the anionic rhodium systems of Union Carbide show any appreciable shift activity. With neutral species of the type M3(CO)12 (M = Ru or Os), only small quantities of carbon dioxide are produced under the synthesis conditions (57). 

Supercritical fluids (e.g. supercritical carbon dioxide, scCCb) are regarded as benign alternatives to organic solvents and there are many examples of their use in chemical synthesis, but usually under homogeneous conditions without the need for other solvents. However, SCCO2 has been combined with ionic liquids for the hydroformylation of 1-octene [16]. Since ionic liquids have no vapour pressure and are essentially insoluble in SCCO2, the product can be extracted from the reaction using CO2 virtually uncontaminated by the rhodium catalyst. This process is not a true biphasic process, as the reaction is carried out in the ionic liquid and the supercritical phase is only added once reaction is complete. 

Supercritical fluids have also been used purely as the solvent for polymerization reactions. Supercritical fluids have many advantages over other solvents for both the synthesis and processing of materials (see Chapter 6), and there are a number of factors that make scCCH a desirable solvent for carrying out polymerization reactions. As well as being cheap, nontoxic and nonflammable, separation of the solvent from the product is achieved simply by depressurization. This eliminates the energy-intensive drying steps that are normally required after the reaction. Carbon dioxide is also chemically relatively inert and hence can be used for a wide variety of reactions. For example, CO2 is inert towards free radicals and this can be important in polymerization reactions since there is then no chain transfer to the solvent. This means that solvent incorporation into the polymer does not take place, giving a purer material. 

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