应用电化学Chapter3.pptVIP

Chapter 3  Electrolytic production  of chemicals Major uses of chlorine and sodium hydroxide: see p174 Table 3.1 a)?????? energy intensive process b)????? serious corrosion and pollution c) chlor-alkali balance 3.1 General concepts  of brine electrolysis Electrode materials can be classified to three type according to values of a: 1) Low-overpotential metals a=0.1~0.3 V, such as Pt, Pd etc. 2) Middle-overpotential metals a=0.5~0.7V, Fe, Co, Ni, Cu, W, Au etc. 3) High-overpotential metals a=1.0~1.5V, Pb, Cd, Hg, An, Bi, Sn etc. How to select electrode materials? We should select materials which have lower value of a to decreaseηH (i.e. Io higher). Why? The mechanism of hydrogen evolution reaction: 1)????? Mass transport 2)????? Electron transfer There are different mechanisms according to different rate-determining step: Slow discharge theory Hence, we should seek appropriate electrode materials and reaction conditions where the overpotential for the desired reaction is low but, in addition, high for possible competing reactions. The difference of overpotentials between chlorine and oxygen reactions should be as large as possible. 2. Cathode reactions 3. Reactions in the solution The importance of separator in the chlor-alkali cells: Separate two departments and retard the transport of OH- from cathodic department to anodic. Other measures: a) T↑, CNaCl↑, solubility of Cl2 decreases b) The liquid level of anode is higher than that of cathode to retard diffusion of OH- to anodic department. 3.1.3 Cell voltage and electric  energy consumption Discussion: a)?? The concentration of salt in anodic region CNaCl↑, ↓, E↓ b)????? Temperature T↑, ↓↓, ↓, E↓ c)????? The concentration of caustic soda CNaOH↑, ↓, E↑ 2. Overpotentials Anode graphite