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Arun.S.

Siddarth

Electrochemical window (EW): Important property of ionic liquids Wide EW makes Ionic liquids stable at extreme potentials. Potential window: Difference between the oxidation and reduction potentials in a particular electrolyte (RTIL in this case) Factors pertaining to potential window and its measurement are discussed here.

CV and LSV: used for EW determination. Lot of complications encountered while comparing the measured voltammogram with reported data even with the same ILs. Measurement conditions, scan rate, limiting CD, reference electrode, IR drop, and RE determine these differences. Presence of impurities also cause drastic changes. High viscosity, and resulting low conductivity, also poses complications in measurement.

Certain CD, called the cut off current: must be established in order to measure the oxidation and reduction potentials. Cathodic and anodic limiting potentials evaluated when the C.D. reaches the chosen cut off value. The cut off C.D. usually selected between 0.1 and 1 mA/sq.cm

Configuration of RE in ILs almost same as organic solvents. RE: redox system with stable potential. EW data (Cathodic and anodic limiting potentials different) with different RE Problem solved by use of internal reference: ferrocene. Redox potential of Fc in RTILs is similar to the RE content. This cancels the junction potential between RE and IL electrolyte

Current proportional to square root of sanc rate in all EC systems Same predictions followed in RTILs Limiting potential at same current density shifted by variation of scan rate Cut off current density changed w.r. to relation to relation btw sq root of scan rate and c.d.

Water and Oxygen: major impurities contained in RTILs. Removal of these molecules- vital for voltmmetric measurement. Glove box with inert gas flow: essential to avid contamination and erroneous measurement. Non volatile nature of RTIL facilitates easy water removal by vacuum drying.

Figure indicates LSV of TMPA-TPSI in Pt working electrode and Fc internal reference containing various amounts of water.

Figure indicates LSV of TMPA-TPSI in GC working electrode and Fc internal reference containing various amounts of water.

Chloroaluminate systems studied widely in electrochemical fields. AlCl3 anion mole fraction: denoted by N N>0.5: acidic, N=0.5: basic, N<0.5 neutral Al wire in acidic melt (N=0.60 to 0.67) : RE EW depends on melt composition Anodic oxidation potential not always determined my anion oxidation

Cathodic limiting potential: basically determined by the reduction of cations Cathodic limiting potential determined by anion reduction in case of poor cathodic stability of cation species Anionic limiting potential basically determined by the oxidation of anions, except in cases where the limiting potential is independent of anions. Aliphatic quaternary ammonium based systems have highest EW. This is attributed to the presence of quaternary ammonium salts high EW (usually used as supporting electrolytes in conventional systems)