On the Transition-State theory approach to the Jones-Dole’s viscosity B-coefficient: A novel molecular-based interpretation, assessment of its implications, and experimental evidence

On the Elusive Links between Solution Microstructure, Dynamics, and Solvation Thermodynamics: Demystifying the Path through a Bridge over Troubled Conjectures and Misinterpretations

“…In Figure , we display the observed dependence of the experimental data B i = ν + B + + ν – B – on the fundamental structure making/breaking function scriptS i H 2 O ∞ ( T , P ) for a set of aqueous electrolytes at T = 298 K and P = 0.1 MPa comprising 2 ≤ (ν + + ν – ) ≤ 6, where we find that most systems fall in the top quadrants of the B i − scriptS i H 2 O ∞ plane, i.e ., where B i ≥ 0 while scriptS i H 2 O ∞ 0. Therefore, the majority of the aqueous salts will exhibit a positive Jones-Dole B –coefficient; however while less frequently, aqueous electrolyte systems might exhibit the opposite behavior, i.e ., B i ≤ 0 while scriptS i H 2 O ∞ 0. , …”

“…It becomes immediately obvious that, the first contribution embodies direct microstructural information on the system at the ground state, while the second contribution represents an integral over the difference of microstructural behavior between the activated state and the ground state of the viscous flow. In fact, this feature leads to the following equivalent expression to eq , B i ( T , P ) = ν z j o false( υ j o scriptS i j ∞ − υ j ‡ , o scriptS i j , η ‡ , ∞ false) ̅ + ν υ j o scriptS i j ∞ where z j o = β P υ j o identifies the compressibility factor of the pure j –solvent at the prevailing ( T , P ) state conditions, and false( υ j o scriptS i j ∞ − υ j , η ‡ , o scriptS i j , η ‡ , ∞ false) ̅  P − 1 ∫ 0 P ( υ ...…”

“…Indeed, any specific ion effect becomes always constrained by the electroneutrality (zeroth moment for each ion) and the Stillinger-Lovett (second moment) conditions for the ion–ion distribution functions , anion- and cation-specific effects cannot be treated as independent eventswhile simultaneously, the ion distributions are state condition and concentration dependent. In other words, any effort toward gaining insights into the electrolyte solute-induced effects through rules of thumb markers, including those based on the sign of either Jones–Dole’s viscosity B i – and Engel–Hertz’s diffusion B i ’ –coefficient of individual ions, or Hepler’s thermal expansivity of the salt, appears fruitless and misguided as critically discussed elsewhere. − …”

“…84,87 By noticing that eqs 54 and 63 involve the same microstructural component, and consequently, the same f undamental structure making/breaking f unction ij , i.e.,…”