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@ARTICLE{Fritsch:1007314,
author = {Fritsch, Birk and Körner, Andreas and Couasnon, Thaïs and
Blukis, Roberts and Taherkhani, Mehran and Benning, Liane G.
and Jank, Michael P. M. and Spiecker, Erdmann and Hutzler,
Andreas},
title = {{T}ailoring the {A}cidity of {L}iquid {M}edia with
{I}onizing {R}adiation: {R}ethinking the {A}cid–{B}ase
{C}orrelation beyond p{H}},
journal = {The journal of physical chemistry letters},
volume = {14},
number = {20},
issn = {1948-7185},
address = {Washington, DC},
publisher = {ACS},
reportid = {FZJ-2023-02004},
pages = {4644 - 4651},
year = {2023},
abstract = {Advanced in situ techniques based on electrons and X-rays
are increasingly used to gain insights into fundamental
processes in liquids. However, probing liquid samples with
ionizing radiation changes the solution chemistry under
observation. In this work, we show that a radiation-induced
decrease in pH does not necessarily correlate to an increase
in acidity of aqueous solutions. Thus, pH does not capture
the acidity under irradiation. Using kinetic modeling of
radiation chemistry, we introduce alternative measures of
acidity (radiolytic acidity π* and radiolytic ion product
KW*), that account for radiation-induced alterations of both
H+ and OH– concentration. Moreover, we demonstrate that
adding pH-neutral solutes such as LiCl, LiBr, or LiNO3 can
trigger a significant change in π*. This provides a huge
parameter space to tailor the acidity for in situ
experiments involving ionizing radiation, as present in
synchrotron facilities or during liquid-phase electron
microscopy.},
cin = {IEK-11},
ddc = {530},
cid = {I:(DE-Juel1)IEK-11-20140314},
pnm = {1122 - Design, Operation and Digitalization of the Future
Energy Grids (POF4-112) / GRK 1896 - GRK 1896:
In-situ-Mikroskopie mit Elektronen, Röntgenstrahlen und
Rastersonden (218975129) / DFG project 53244630 - EXC 315:
Neue Materialien und Prozesse - Hierarchische
Strukturbildung für funktionale Bauteile (53244630)},
pid = {G:(DE-HGF)POF4-1122 / G:(GEPRIS)218975129 /
G:(GEPRIS)53244630},
typ = {PUB:(DE-HGF)16},
pubmed = {37167107},
UT = {WOS:001014119300001},
doi = {10.1021/acs.jpclett.3c00593},
url = {https://juser.fz-juelich.de/record/1007314},
}