Abstract
X‐ray structural data, 
evolution overpotentials 
, and rate constants 
are compared for anodic oxidation of Mn(II) 
and 2‐thiophene carboxylic acid (2‐TCA) at Bi‐doped 
in 
. It is concluded that the rutile structure of pure 
deposited anodically from 
containing Pb(II) is retained even as the Bi(III) content is increased to 
, i.e., mole fraction 
. There is no evidence of a new oxide phase being formed. Crystallites of the 
are deposited with an increasing preferential orientation of the 020‐plane parallel to the Au substrate surface as the ratio Bi/Pb is increased. Increasing values of 
and decreasing values of 
appear to be correlated with the increased preferential orientation. However, change in preferential orientation is concluded not to be the primary determining factor in the electrocatalytic phenomena. The kinetic results are discussed also on the basis of the so‐called "volcano plot" of 
as a function of the enthalpy of transition 
between the two highest oxide phases for metal oxide electrodes.