Thermodynamic Study of Cadmium Chloride in Aqueous Mixtures of 2-Butanol from Potential Difference Measurements

The standard molal potential differences (E_m∘) have been determined for the cell: CdHg_x(two phase) | CdCl₂(m), H₂O(1 − w), 2-butanol (w) | AgCl(s) | Ag(s) in aqueous mixtures of low mass fraction of 2-butanol (w_2-butanol = 0.05, 0.10, and 0.15) by using the literature data for the stability constants of the chlorocadmium complexes and the present potentiometric data for this cell at five temperatures from (293.15 to 313.15) K and at 10 molalities of CdCl₂ from (0.002 to 0.02) mol-kg⁻¹. The resulting values of E∘_m have been used to calculate the standard thermodynamic quantities (Δ_rG^∘, Δ_rH^∘, and Δ_rS^∘) for the cell reaction, the stoichiometric mean molal activity coefficients (γ_±) of CdCl₂, and the standard thermodynamic functions for CdCl₂ transfer (Δ_t G∘, Δ_t H∘, and Δ_t S∘) from water to the examined aqueous mixtures of 2-butanol. The values obtained have been compared with the analogous literature data for aqueous mixtures of 2-butanone; standard thermodynamic quantities for transfer of CdCl₂ and HBr from water to mixtures containing the same mass fraction of 2-butanol have also been compared. For both electrolytes, these quantities show analogous trends with the alcohol content. This transfer process is nonspontaneous and endothermic. Enthalpy and entropy are evidently influenced by structural changes.