The unambiguous quantification of the proton transfer in Protic Ionic Liquids (PILs) and its differentiation from the concept of ionicity are still unsolved questions. Albeit researchers awfully quickly treat them as synonyms, the two concepts are intrinsically different and imply a dramatic modification in the expected chemical and physical properties of a PIL. Some attempts have been made to shed light on this discrimination, but single-technique-based approaches fail in giving a clear answer. Aiming at definitively figuring out the differentiation between proton transfer and ionicity, we performed a multi-technique analysis (NMR, Raman, IR, thermal and electrochemical analyses, among others). Indeed, thermal and spectroscopic analyses are employed to determine the acid strength's role in ions' complete formation. To overcome the ambiguity between ionicity and formation degree, we introduce a new paradigm where Reduced Ionicity accounts for both the quantities mentioned above. The reduced ionicity directly affects the thermal stability, the phase behavior, and the spectroscopic observations, resulting in particular features in NMR and vibrational spectra. The combination of physical-chemical analyses and Pulsed-Gradient Spin-Echo (PGSE) NMR allows determining the reduced ionicity (and not the ionicity, as reported so far) of the investigated systems. In this context, being the proton transfer not quantitatively accessible directly, the reduced ionicity of a reference series of triethylamine-based PILs is investigated through transport properties as a function of temperature. Our findings point towards a substantial dependence of the reduced ionicity by the acid strength and the anion's coordination power. Furthermore, some interesting insights about the proton transfer are obtained, combining all the findings collected. (C) 2020 Elsevier B.V. All rights reserved.

Mariani, A., Bonomo, M., Gao, X., Centrella, B., Nucara, A., Buscaino, R., et al. (2021). The unseen evidence of reduced ionicity: the elephant in (the) room temperature ionic liquids. JOURNAL OF MOLECULAR LIQUIDS, 324 [10.1016/j.molliq.2020.115069].

The unseen evidence of reduced ionicity: the elephant in (the) room temperature ionic liquids

Gontrani L.
Validation
;
2021-01-01

Abstract

The unambiguous quantification of the proton transfer in Protic Ionic Liquids (PILs) and its differentiation from the concept of ionicity are still unsolved questions. Albeit researchers awfully quickly treat them as synonyms, the two concepts are intrinsically different and imply a dramatic modification in the expected chemical and physical properties of a PIL. Some attempts have been made to shed light on this discrimination, but single-technique-based approaches fail in giving a clear answer. Aiming at definitively figuring out the differentiation between proton transfer and ionicity, we performed a multi-technique analysis (NMR, Raman, IR, thermal and electrochemical analyses, among others). Indeed, thermal and spectroscopic analyses are employed to determine the acid strength's role in ions' complete formation. To overcome the ambiguity between ionicity and formation degree, we introduce a new paradigm where Reduced Ionicity accounts for both the quantities mentioned above. The reduced ionicity directly affects the thermal stability, the phase behavior, and the spectroscopic observations, resulting in particular features in NMR and vibrational spectra. The combination of physical-chemical analyses and Pulsed-Gradient Spin-Echo (PGSE) NMR allows determining the reduced ionicity (and not the ionicity, as reported so far) of the investigated systems. In this context, being the proton transfer not quantitatively accessible directly, the reduced ionicity of a reference series of triethylamine-based PILs is investigated through transport properties as a function of temperature. Our findings point towards a substantial dependence of the reduced ionicity by the acid strength and the anion's coordination power. Furthermore, some interesting insights about the proton transfer are obtained, combining all the findings collected. (C) 2020 Elsevier B.V. All rights reserved.
2021
Pubblicato
Rilevanza internazionale
Articolo
Esperti anonimi
Settore CHIM/02 - CHIMICA FISICA
English
Ionicity; Proton transfer; PGSE-NMR; PGSE-NMR; Protic ionic liquids; Vibrational spectroscopy; Triethylammonium
Mariani, A., Bonomo, M., Gao, X., Centrella, B., Nucara, A., Buscaino, R., et al. (2021). The unseen evidence of reduced ionicity: the elephant in (the) room temperature ionic liquids. JOURNAL OF MOLECULAR LIQUIDS, 324 [10.1016/j.molliq.2020.115069].
Mariani, A; Bonomo, M; Gao, X; Centrella, B; Nucara, A; Buscaino, R; Barge, A; Barbero, N; Gontrani, L; Passerini, S
Articolo su rivista
File in questo prodotto:
File Dimensione Formato  
1-s2.0-S0167732220373116-main.pdf

solo utenti autorizzati

Tipologia: Versione Editoriale (PDF)
Licenza: Copyright dell'editore
Dimensione 1.88 MB
Formato Adobe PDF
1.88 MB Adobe PDF   Visualizza/Apri   Richiedi una copia

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: https://hdl.handle.net/2108/293770
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 29
  • ???jsp.display-item.citation.isi??? 28
social impact