Adsorption of bromide and iodide anions on a renewable liquid (Cd–Ga) electrode from acetonitrile solutions. Effect of (Cd–Ga)–solvent chemisorption interaction on the anion adsorption energy

The specific adsorption of bromide and iodide anions was studied at a (Cd–Ga)/acetonitrile (AN) interface from mixed solutions of [0.1 m M LiBr + 0.1 (1–m) M LiBF4] and [0.1 m M LiI + 0.1 (1–m) M LiBF4] at the following values of molar fraction m of the surface–active anion: 0, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, and 1. The main experimental method was measurement of differential capacitance on a renewable liquid (Cd–Ga) electrode. The obtained experimental results can be described quantitatively by the Frumkin isotherm in a wide range of charge densities (σ). The adsorption parameters of halide anions (Hal−) were determined using regression analysis of two-dimensional pressure isotherms. It is shown that the adsorption energies (ΔGads) of Br− and I− at the (Cd–Ga)/AN interface practically coincide. It follows that the difference in the interaction energies of Br− and I− with (Cd–Ga) is equal to the difference of the solvation energies of these anions: (ΔG(Cd‐Ga)‐Br‐ − ΔG(Cd‐Ga)‐I‐)≈(ΔGAN‐Br‐ − ΔGAN‐I‐) and therefore ΔG(Cd-Ga)-I− < ΔG(Cd-Ga)-Br−. The adsorption parameters of Hal− obtained on the (Cd–Ga)/AN interface are compared with the similar data for the (Cd–Ga)/DMF interface. The adsorption energy of Br− and I− on a (Cd–Ga) electrode increases significantly in AN as compared to DMF. This result can be unambiguously explained by a significant decrease in the energy of chemisorption interaction between a (Cd–Ga) electrode and solvent molecules in the Helmholtz layer upon transition from DMF to AN. The ΔGads,σ-dependence obtained at the (Cd–Ga)/AN interface in the first approximation characterizes the change of the free energy of (Cd–Ga)–Hal− interaction with σ. It is shown that the slope of the ΔGads, σ-dependence decreases upon transition from the (Cd–Ga)/AN interface to the (Cd–Ga)/DMF interface due to a significant increase in the energy of the chemisorption interaction of (Cd–Ga) with DMF molecules in the Helmholtz layer during the transition from negative to positive values of charge density. [Display omitted] •Adsorption of Hal− at the (Cd–Ga)/AN can be described by Frumkin isotherm.•The values of ΔGads at the (Cd–Ga)/AN for Br− and I− practically coincide.•From the data obtained it follows that ΔG(Cd-Ga)-I− < ΔG(Cd-Ga)-Br−.•ΔGads of Hal− increase at transition from (Cd–Ga)/DMF to (Cd–Ga)/AN.•Slope of the ΔGads,σ-dependence decreases upon a transition from AN to DMF.