The determination of the chemical diffusion coefficients for AgBr and .ALPHA.-AgI by means of an improved d.c. polarization cell.

概要

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In order to determine the chemical diffusion coefficients for AgBr and α-AgI, a new experimental technique was developed. A Pt probe was inserted into the middle of the AgX (X=Br or I) pellet in an improved d.c. polarization cell of the Ag/AgX/carbon type, and the applied potential difference between the Ag and carbon electrodes was changed abruptly. The accompanying change in E(L⁄2), the EMF between the Ag electrode and the Pt prcbe, was followed, and the cherrical diffusion coefficient, \tildeD, was determined by the analysis of the change in E(L⁄2) with the time. In the temperature range from 325 to 400 °C, \tildeD for AgBr with excess silver was found to be \tildeD=7.10×102exp\left(−\frac1.96×104 cal molRT\right)cm2s−1. (i) In the temperature range of 330 to 500 °C, \tildeD for a-AgI was \tildeD=4.95×10−1exp\left(−\frac7.71×103 cal mol−1RT\right)cm2s−1. (ii) Using these chemical diffusion coefficients and the electronic conductivity data, the nonstoichiomctry, and apparent mobility of electronic carriers of AgBr and α-AgI were determined.
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