용융 (60 몰% $AlCl_3$-40 몰% NaCl) 염 속에서의 알루미늄전극의 반응속도론적 연구

A Kinetic Study of the Aluminum Electrode in Molten 60 Mole Percent $AlCl_3$-40 Mole Percent NaCl at 453${\circ}K$

  • G. F. Uhlig (Department of Chemistry, University of Utah) ;
  • T. N. Andersen (Department of Chemistry, University of Utah) ;
  • S. Johns (Department of Chemistry, University of Utah) ;
  • H. Eyring (Department of Chemistry, University of Utah)
  • 발행 : 1974.12.30

초록

60몰%$AlCl_3$-40몰% NaCl의 용융염($453^{\circ}$<\TEX>K)속에든 알루미늄 전극에 대하여 전류-전압 편극곡선을 얻었다. 50mA/$CM^2$보다 큰 전류밀도에서는 옴-저항에 의한 전위차가 양극전위에 상당히 기여하므로 저항이 큰 $AlCl_3$(혹은 $AlCl_3$ 의 농도가 큰 멜트)의 층이 양극표면에 가까이 형성된다고 결론지었다. IR-전위차에 대하여 보정한 후의 Tafel곡선과 Allen-Hickling 곡선으로 부터 겉보기 transfer-coefficient, ${\alpha}_a$=(2.3RT/F)(dlogi/d${\eta}$)=$1.5{\pm}0.25$가 얻어졌다. 약 30mA/$cm^2$보다 큰 음극전류밀도에서는 느린 이온확산과 dendrite 생장 때문에 속도론적 측정이 방해 받았다.

Steady-state anodic and cathodic polarization curves were developed for the Al electrode in 60 mole %$AlCl_3$-40 mole % NaCl at $180^{\circ}C$$453^{\circ}K$). Ohmic resistance contributed substantially to the anodic polarization at current densities greater than 50 mA/$CM^2$ even with capillary tip placed close to the electrode. This could not be rationalized from the resistivity of the melt, which would lead to a much smaller polarization. It was therefore concluded that a layer of high resistance $AlCl_3$ (or $AlCl_3$-rich melt) formed close to the anode surface. From the IR-corrected anodic Tafel and Allen-Hickling plots an apparent anodic charge-transfer coefficient of ${\alpha}_a$ = (2.3 RT/F)(d log i/d${\eta}$) = $1.5{\pm}0.25$ was obtained. At cathodic current densities greater than approximately 30 mA/$cm^2$, slow ion diffusion and dendrite growth both interfered with the measurement of kinetic parameters.

키워드

참고문헌

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