The Henderson equation is usually used to calculate liquid-junction potentials between miscible electrolyte solutions. However, the potentials of reference electrodes that comprise an electrolyte-filled nanoporous glass frit may also be affected by charge screening. As reported previously, when the Debye length approaches or surpasses the glass pore diameter, reference potentials depend on the composition of the bridge electrolyte, the pore size of the frit, and the concentration of electrolyte in the sample. We report here that stirring of samples may alter the reference potential as it affects the electrolyte concentration in the section of the nanoporous glass frit that is facing the sample solution. When the flow rate of bridge electrolyte into the sample is small, convective mass transport of sample into the nanoporous frit occurs. The depth of penetration into the frit is only a few nanometers but, despite the use of concentrated salt bridges, this is enough to affect the extent of electrostatic screening when samples of low ionic strength are measured. Mixing of sample and salt bridge solutionsand in particular penetration of sample components into the fritwas optically monitored by observation of a deeply colored Fe[(SCN)(H 2 O) 5 ] 2+ complex that formed in situ exclusively in the region where the sample and salt bridge mixed. Importantly, because flow through nanoporous frits is very slow, mass transport through these frits is dominated by diffusion. Consequently, over as little as 1 h, reference electrode frits with low flow rates become contaminated with sample components and undergo depletion of electrolyte within the frit to a depth of several millimeters, which can negatively affect subsequent experiments.

An attempt has been made to study the influence of magnetic field on the micro hole machining of Ti-6Al-4V titanium alloy using electrochemical micromachining (ECMM) process. The presence of magneto hydro dynamics (MHD) is accomplished with the aid of external magnetic field (neodymium magnets) in order to improve the machining accuracy and the performance characteristics of ECMM. Close to ideal solution for magnetic and nonmagnetic field ECMM process, the parameters used are as follows: concentration electrolyte of 15 g/l; peak current of 1.35 A; pulse on time of 400 s; and duty factor of 0.5. An improvement of 11.91–52.43% and 23.51–129.68% in material removal rate (MRR) and 6.03–21.47% and 18.32–33.09% in overcut (OC) is observed in ECMM of titanium alloy under the influence of attraction and repulsion magnetic field, respectively, in correlation with nonmagnetic field ECMM process. A 55.34% surface roughness factor reduction is ascertained in the hole profile in magnetic field-ECMM in correlation with electrochemical machined titanium alloy under nonmagnetic field environment. No machining related stress is induced in the titanium alloy, even though environment of electrochemical machining process has been enhanced with the presence of magnetic field. A slight surge in the compressive residual factor, aids in surge of passivation potential of titanium alloy, resulting in higher resistance to outside environment.