Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 120, Issue 32, Pages 18099-18104Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.6b05564
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Funding
- Natural Sciences and Engineering Research Council of Canada
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We observed that the structure of water in the Stern layer depends on the identity of the cation, which cannot be predicted with classical double layer models. The ability of a cation to displace the hydration water on a silica suffice is in the order of Mg2+ > Ca2+ > Li+ > Na+, which is consistent with the trend of the acid dissociation constant (K-a) of the salt. Our data suggest that ions with a high pK(a), such as Mg2+ and Ca2+, have a local electrostatic field strong enough to polarize water molecules in the hydration shells of the ions which form linkages with the negative charges on the silica, Si-O-center dot center dot center dot H+delta center dot center dot center dot OH-delta center dot center dot center dot M2+, and displace the hydration water on the silica surface. Ions with a low pK(a), such, as Na+ and Li+, are unable to displace the hydration water on the silica surface.
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