Chapter 3 Electrolytic production of chemicals 应用电化学 知识讲稿.pptVIP

3.3 Modern technological developments 1.? Anodes The basic requirements for electrode materials: 1) be stable 2) high current efficiency, low overpotential (1) Graphite The overpotential for Cl2 evolution was as high as 500mV and the wear rate 2-3kg of anode carbon per ton chlorine. (2) DSA (dimensionally stable anode) H.B. Beer, in the early 1960s Advantages: a) High electrocatalysis activity In comparison to graphite anode, the overpotential for Cl2 decreases by 90% (50mV) b) Stable They are inert and very stable to corrosion and their service lifetime can be 6~8 years( graphite anode about 8 months). c) The current density can be increase due to low over-potential, so as to increase space-time yield. DSAs are now a family of coatings which applied to titanium. The coatings are based on ruthenium dioxide but they may also contain valve metal, precious metal or transition metal oxides to improve performance. Generally they are prepared by spraying a mixture of chlorides in an alcohol, commonly isopropanol, and then heating in air. 2.?????? Cathodes The cathode in diaphragm cells was traditionally mild steel, which was very sable to corrosion but gave rise to an overpotential of 300-500mV. Precious metal coatings on a nickel base and high nickel coatings: overpotential as low as 50mV. 3.???Diaphragm/membrane The perfect separator in a chlor-alkali cell would: 1) pass sodium ions (but no protons) from anolyte to catholyte without the transport of chloride ion (leads to Cl- contamination of the NaOH) or hydroxide ion from catholyte to anolyte (causes loss of NaOH and O2 contamination of the Cl2) 2) have a low resistance 3) be stable to wet chlorine and 50% sodium hydroxide over a long period of time. (1) Diahpragm A diaphragm is porous and cannot discriminate between species. Asbestos diaphragm (2) Membrane cation exchange membranes see pp181-183 Exercise: w