The effect of temperature on ion transfer across the water-nitrobenzene interface was studied for a series of six quaternary ammonium and phosphonium cations and two anions using cyclic voltammetry and the faradaic impedance method at the equilibrium potential. Structure-breaking properties of small ions and enhancement of water structure in the presence of larger cations were manifested in both entropic and enthalpic contributions to the standard Gibbs energy of ion transfer. At the phase boundary, the ion is forced to overcome a relatively low potential barrier of about 5 kJ mol-1, but the ion transfer rate is lowered considerably owing to hydrodynamic friction. The hydrodynamic factor of about 10(-4) reflects a drop in ion mobility in the transition state, which in turn makes the translational part of the activation entropy more negative. The stochastic method has provided a consistent theory for experimentally observed effects of interfacial potential difference, standard Gibbs energy of ion transfer (Bronsted correlation). viscosity and temperature.

Effect of temperature on the ion transfer across an interfaces between two immiscible electrolyte solution. Ion transfer dynamics

FUOCO, ROGER
1992

Abstract

The effect of temperature on ion transfer across the water-nitrobenzene interface was studied for a series of six quaternary ammonium and phosphonium cations and two anions using cyclic voltammetry and the faradaic impedance method at the equilibrium potential. Structure-breaking properties of small ions and enhancement of water structure in the presence of larger cations were manifested in both entropic and enthalpic contributions to the standard Gibbs energy of ion transfer. At the phase boundary, the ion is forced to overcome a relatively low potential barrier of about 5 kJ mol-1, but the ion transfer rate is lowered considerably owing to hydrodynamic friction. The hydrodynamic factor of about 10(-4) reflects a drop in ion mobility in the transition state, which in turn makes the translational part of the activation entropy more negative. The stochastic method has provided a consistent theory for experimentally observed effects of interfacial potential difference, standard Gibbs energy of ion transfer (Bronsted correlation). viscosity and temperature.
Wandlowsky, T.; Marecek, V.; Samec, Z.; Fuoco, Roger
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11568/18074
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 44
  • ???jsp.display-item.citation.isi??? 0
social impact