Cathode efficiency temperature effect

Figure 12.5. Effect of temperature on cathode efficiency. (From Ref. 4, with permission from Wiley.)...

To illustrate and clarify the foregoing, we discuss the case of cyanide-zinc plating baths. Those are operated at less than 100% cathode efficiency. In a quantitative sense, typical plating baths show a functional behavior as illustrated in Figures 12.4 and 12.5, where we present the effects of temperature and cyanide Zn concentration ratio on cathode efficiency versus cathode current density. 

First, it is instructive to examine the performance of a recuperated system that has only one compressor (i.e., remove the IC and C2 from Figure 8.2) and compare this to a simple cycle GT (i.e., also remove the recuperator from the diagram). Consider an isentropic compressor efficiency of 85%, isentropic turbine expander efficiency of 90%, recuperator effectiveness of 88% and no pressure losses. A fixed turbine inlet temperature of 1200 K will be assumed for various pressure ratios. This value is based on an assumed 1000 K SOFC inlet temperature, and a 200 K temperature rise from the SOFC inlet to the turbine inlet. The 200 K temperature increase from the cathode inlet to the turbine inlet is reasonable to assume given a cathode temperature difference across the cell of 150 K, and another 50 K temperature increase from anode exhaust combustion. Thus, 1200 K will be used as a base case for the turbine inlet temperature, and for sensitivity, values of 1100 and 1300 K will also be analyzed. 

A similar distinction between a system with pre-electrolysis with only one electrode (in this case anodic) process, and a system with simultaneous anodic and cathodic processes (in which anode and cathode are on opposite walls of a microchannel so that each liquid is only in contact with the desired electrode potential, analogous to the fuel cell configurations discussed above) was made by Horii et al. (2008) in their work on the in situ generation of carbocations for nucleophilic reactions. The carbocation is formed at the anode, and the reaction with the nucleophile is either downstream (in the pre-electrolysis case) or after diffusion across the liquid-liquid interface (in the case with both electrodes present at opposite walls). The concept was used for the anodic substitution of cyclic carbamates with allyltrimethylsilane, with moderate to good conversion yields without the need for low-temperature conditions. The advantages of the approach as claimed by the authors are efficient nucleophilic reactions in a single-pass operation, selective oxidation of substrates without oxidation of nucleophile, stabilization of cationic intermediates at ambient temperatures, by the use of ionic liquids as reaction media, and effective trapping of unstable cationic intermediates with a nucleophile. 

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