Local molecular environment drives speciation and reactivity of ion complexes in concentrated salt solution

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60076658%3A12310%2F21%3A43902982" target="_blank" >RIV/60076658:12310/21:43902982 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388963:_____/21:00545501

Výsledek na webu

<a href="https://www.sciencedirect.com/science/article/pii/S0167732221016226?via%3Dihub" target="_blank" >https://www.sciencedirect.com/science/article/pii/S0167732221016226?via%3Dihub</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.molliq.2021.116898" target="_blank" >10.1016/j.molliq.2021.116898</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Local molecular environment drives speciation and reactivity of ion complexes in concentrated salt solution

Popis výsledku v původním jazyce

The speciation and reactivity of aqueous salt solutions are important for a wide variety of applications. However, application of this information is inhibited by broad disagreement about composition, mechanisms, and structure in concentrated solutions especially. Here, neutron diffraction with isotopic substitution measurements on aqueous zinc chloride solutions are used to calibrate molecular dynamics simulations that include effective electronic polarization. This allows us to probe the origin of speciation and reactivity of zinc chloride-water ion complexes, ZnClx(H2O)(y)(2-x) (x &lt;= 4 and y &lt;= 6), by comparing the reactivity of species in concentrated (4.5 m) and dilute (0.01 m) conditions. Within the concentrated solution, it is found that the extended solvation environment is dominated by solvent-separated ion complexes whose presence increases the free energy of activation for interconversion of species while simultaneously enhancing their thermodynamic stability. This concentration-dependent reactivity and stability suggests that other reactions, such as the nucleation of solid phases, will also be affected. (C) 2021 The Authors. Published by Elsevier B.V.

Název v anglickém jazyce

Local molecular environment drives speciation and reactivity of ion complexes in concentrated salt solution

Popis výsledku anglicky

The speciation and reactivity of aqueous salt solutions are important for a wide variety of applications. However, application of this information is inhibited by broad disagreement about composition, mechanisms, and structure in concentrated solutions especially. Here, neutron diffraction with isotopic substitution measurements on aqueous zinc chloride solutions are used to calibrate molecular dynamics simulations that include effective electronic polarization. This allows us to probe the origin of speciation and reactivity of zinc chloride-water ion complexes, ZnClx(H2O)(y)(2-x) (x &lt;= 4 and y &lt;= 6), by comparing the reactivity of species in concentrated (4.5 m) and dilute (0.01 m) conditions. Within the concentrated solution, it is found that the extended solvation environment is dominated by solvent-separated ion complexes whose presence increases the free energy of activation for interconversion of species while simultaneously enhancing their thermodynamic stability. This concentration-dependent reactivity and stability suggests that other reactions, such as the nucleation of solid phases, will also be affected. (C) 2021 The Authors. Published by Elsevier B.V.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/LTAUSA17163" target="_blank" >LTAUSA17163: Molekulární simulace procesů na rozhraní pevná látka - kapalina</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Molecular Liquids

ISSN

0167-7322

e-ISSN

—

Svazek periodika

340

Číslo periodika v rámci svazku

OCT 15 2021

Stát vydavatele periodika

BE - Belgické království

Počet stran výsledku

10

Strana od-do

—

Kód UT WoS článku

000696603300078

EID výsledku v databázi Scopus

2-s2.0-85110765741