Acidity and Phase Behavior of Frozen Hydrochloric Acid during
Thawing

J 2024

Acidity and Phase Behavior of Frozen Hydrochloric Acid during Thawing

ŠTŮSEK, Radim; Lukáš VESELÝ; Markéta MELICHAROVÁ; Jan ZEZULA; Johannes GIEBELMANN et al.

Základní údaje

Originální název

Acidity and Phase Behavior of Frozen Hydrochloric Acid during Thawing

Autoři

ŠTŮSEK, Radim; Lukáš VESELÝ; Markéta MELICHAROVÁ; Jan ZEZULA; Johannes GIEBELMANN; Thomas LOERTING a Dominik HEGER

Vydání

Journal of Physical Chemistry C, Washington D.C. American Chemical Society, 2024, 1932-7447

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 3.200

Označené pro přenos do RIV

Ano

Kód RIV

RIV/00216224:14310/24:00137407

Organizační jednotka

Přírodovědecká fakulta

Klíčová slova anglicky

Basification; Cold crystallization; Concentrated solution; Concentration factors; Freeze concentration; Frozen solutions; ITS applications; Knowledge gaps; Non equilibrium; Scanning calorimetry

Štítky

14313010, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 5. 11. 2024 15:41, Mgr. Pavla Foltynová, Ph.D.

Anotace

V originále

Freezing and its application is growing in popularity, yet the understanding of the nonequilibrium transformations and acidity changes that occur in frozen solutions upon thawing have remained relatively unexplored. By contrast to other acids such as nitric acid and sulfuric acid, not even the phase diagram is known fully for hydrochloric acid. Even more importantly, the nonequilibrium transformations upon heating glassy freeze-concentrated solution (FCS) are also not well understood and freeze concentration lacks quantification. This work rectifies the knowledge gap by providing the freeze-concentration factors on the example of hydrochloric acid. For this purpose, we have used differential scanning calorimetry to reveal phase changes upon heating. UV-vis spectroscopy of acid-base indicators is employed to elucidate acidity changes. All the samples reach negative values of the Hammett acidity function from -2.5 to -0.25 after freezing, showing that aqueous HCl can freeze concentrate 7-250,000 times depending on its initial concentration. We observe the glass-to-liquid transition of the freeze-concentrated glassy solution above -140 degrees C and cold crystallization of the ultraviscous FCS to HCl hydrates above -110 degrees C. Cold crystallization leads to basification, whereas acidification accompanies the subsequent melting of the eutectic ice/HCl-hexahydrate. Finally, melting of the ice immersed in solution shows basification caused by the dilution with meltwater. High (1 M) and low (<10 mM) concentrations freeze homogeneously, whereas intermediate concentrations reveal the presence of freeze-concentrated regions of higher and lower concentrations having distinct glass transition and melting temperatures.

Návaznosti

MUNI/A/1594/2023, interní kód MU

Název: Vývoj metod a instrumentace pro analýzu biologicky významných látek 2024

Investor: Masarykova univerzita, Vývoj metod a instrumentace pro analýzu biologicky významných látek 2024

MUNI/C/0104/2023, interní kód MU

Název: Studie změn kyselosti po zamrazení vybraných vícesytných anorganických solí a kyselin

Investor: Masarykova univerzita, Studie změn kyselosti po zamrazení vybraných vícesytných anorganických solí a kyselin, Podpora vynikajících diplomových prací

Citovat

ŠTŮSEK, Radim; Lukáš VESELÝ; Markéta MELICHAROVÁ; Jan ZEZULA; Johannes GIEBELMANN; Thomas LOERTING a Dominik HEGER. Acidity and Phase Behavior of Frozen Hydrochloric Acid during Thawing. Journal of Physical Chemistry C. Washington D.C.: American Chemical Society, 2024, roč. 128, č. 41, s. 17674-17685. ISSN 1932-7447. Dostupné z: https://doi.org/10.1021/acs.jpcc.4c04540.

@article{2445945,
   author = {Štůsek, Radim and Veselý, Lukáš and Melicharová, Markéta and Zezula, Jan and Giebelmann, Johannes and Loerting, Thomas and Heger, Dominik},
   article_location = {Washington D.C.},
   article_number = {41},
   doi = {https://doi.org/10.1021/acs.jpcc.4c04540},
   keywords = {Basification; Cold crystallization; Concentrated solution; Concentration factors; Freeze concentration; Frozen solutions; ITS applications; Knowledge gaps; Non equilibrium; Scanning calorimetry},
   language = {eng},
   issn = {1932-7447},
   journal = {Journal of Physical Chemistry C},
   title = {Acidity and Phase Behavior of Frozen Hydrochloric Acid during Thawing},
   url = {https://pubs.acs.org/doi/10.1021/acs.jpcc.4c04540},
   volume = {128},
   year = {2024}
}

TY  - JOUR
ID  - 2445945
AU  - Štůsek, Radim - Veselý, Lukáš - Melicharová, Markéta - Zezula, Jan - Giebelmann, Johannes - Loerting, Thomas - Heger, Dominik
PY  - 2024
TI  - Acidity and Phase Behavior of Frozen Hydrochloric Acid during Thawing
JF  - Journal of Physical Chemistry C
VL  - 128
IS  - 41
SP  - 17674-17685
EP  - 17674-17685
PB  - American Chemical Society
SN  - 19327447
KW  - Basification
KW  - Cold crystallization
KW  - Concentrated solution
KW  - Concentration factors
KW  - Freeze concentration
KW  - Frozen solutions
KW  - ITS applications
KW  - Knowledge gaps
KW  - Non equilibrium
KW  - Scanning calorimetry
UR  - https://pubs.acs.org/doi/10.1021/acs.jpcc.4c04540
N2  - Freezing and its application is growing in popularity, yet the understanding of the nonequilibrium transformations and acidity changes that occur in frozen solutions upon thawing have remained relatively unexplored. By contrast to other acids such as nitric acid and sulfuric acid, not even the phase diagram is known fully for hydrochloric acid. Even more importantly, the nonequilibrium transformations upon heating glassy freeze-concentrated solution (FCS) are also not well understood and freeze concentration lacks quantification. This work rectifies the knowledge gap by providing the freeze-concentration factors on the example of hydrochloric acid. For this purpose, we have used differential scanning calorimetry to reveal phase changes upon heating. UV-vis spectroscopy of acid-base indicators is employed to elucidate acidity changes. All the samples reach negative values of the Hammett acidity function from -2.5 to -0.25 after freezing, showing that aqueous HCl can freeze concentrate 7-250,000 times depending on its initial concentration. We observe the glass-to-liquid transition of the freeze-concentrated glassy solution above -140 degrees C and cold crystallization of the ultraviscous FCS to HCl hydrates above -110 degrees C. Cold crystallization leads to basification, whereas acidification accompanies the subsequent melting of the eutectic ice/HCl-hexahydrate. Finally, melting of the ice immersed in solution shows basification caused by the dilution with meltwater. High (1 M) and low (<10 mM) concentrations freeze homogeneously, whereas intermediate concentrations reveal the presence of freeze-concentrated regions of higher and lower concentrations having distinct glass transition and melting temperatures.
ER  -

ŠTŮSEK, Radim; Lukáš VESELÝ; Markéta MELICHAROVÁ; Jan ZEZULA; Johannes GIEBELMANN; Thomas LOERTING a Dominik HEGER. Acidity and Phase Behavior of Frozen Hydrochloric Acid during Thawing. \textit{Journal of Physical Chemistry C}. Washington D.C.: American Chemical Society, 2024, roč.~128, č.~41, s.~17674-17685. ISSN~1932-7447. Dostupné z: https://doi.org/10.1021/acs.jpcc.4c04540.

Přehled o publikaci