Details
| Original language | English |
|---|---|
| Pages (from-to) | 3535-3541 |
| Number of pages | 7 |
| Journal | CHEMPHYSCHEM |
| Volume | 17 |
| Issue number | 21 |
| Publication status | Published - 4 Nov 2016 |
| Externally published | Yes |
Abstract
The understanding of the molecular mechanisms underlying the early stages of crystallisation is still incomplete. In the case of calcium carbonate, experimental and computational evidence suggests that phase separation relies on so-called pre-nucleation clusters (PNCs). A thorough thermodynamic analysis of the enthalpic and entropic contributions to the overall free energy of PNC formation derived from three independent methods demonstrates that solute clustering is driven by entropy. This can be quantitatively rationalised by the release of water molecules from ion hydration layers, explaining why ion association is not limited to simple ion pairing. The key role of water release in this process suggests that PNC formation should be a common phenomenon in aqueous solutions.
Keywords
- calcium carbonate, entropy, ion association, ion pairing, pre-nucleation clusters
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Atomic and Molecular Physics, and Optics
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: CHEMPHYSCHEM, Vol. 17, No. 21, 04.11.2016, p. 3535-3541.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Entropy Drives Calcium Carbonate Ion Association
AU - Kellermeier, Matthias
AU - Raiteri, Paolo
AU - Berg, John K.
AU - Kempter, Andreas
AU - Gale, Julian D.
AU - Gebauer, Denis
N1 - Funding information: The authors thank H. P. Kaub and S. Deck (BASF SE) for help with some of the ITC measurements. D.G. is supported by the Zukunftskolleg of the University of Konstanz and the Fonds der Chemischen Industrie. D.G. and J.K.B. acknowledge generous support of the Young Scholar Fund of the University of Konstanz. P.R. and J.D.G. acknowledge funding from the Australian Research Council (FT130100463, DP160100677) and the use of resources provided by the Pawsey Supercomputing Centre and the National Computational Infrastructure with funding from the Australian Government and the Government of Western Australia.
PY - 2016/11/4
Y1 - 2016/11/4
N2 - The understanding of the molecular mechanisms underlying the early stages of crystallisation is still incomplete. In the case of calcium carbonate, experimental and computational evidence suggests that phase separation relies on so-called pre-nucleation clusters (PNCs). A thorough thermodynamic analysis of the enthalpic and entropic contributions to the overall free energy of PNC formation derived from three independent methods demonstrates that solute clustering is driven by entropy. This can be quantitatively rationalised by the release of water molecules from ion hydration layers, explaining why ion association is not limited to simple ion pairing. The key role of water release in this process suggests that PNC formation should be a common phenomenon in aqueous solutions.
AB - The understanding of the molecular mechanisms underlying the early stages of crystallisation is still incomplete. In the case of calcium carbonate, experimental and computational evidence suggests that phase separation relies on so-called pre-nucleation clusters (PNCs). A thorough thermodynamic analysis of the enthalpic and entropic contributions to the overall free energy of PNC formation derived from three independent methods demonstrates that solute clustering is driven by entropy. This can be quantitatively rationalised by the release of water molecules from ion hydration layers, explaining why ion association is not limited to simple ion pairing. The key role of water release in this process suggests that PNC formation should be a common phenomenon in aqueous solutions.
KW - calcium carbonate
KW - entropy
KW - ion association
KW - ion pairing
KW - pre-nucleation clusters
UR - http://www.scopus.com/inward/record.url?scp=84987623862&partnerID=8YFLogxK
U2 - 10.1002/cphc.201600653
DO - 10.1002/cphc.201600653
M3 - Article
VL - 17
SP - 3535
EP - 3541
JO - CHEMPHYSCHEM
JF - CHEMPHYSCHEM
SN - 1439-4235
IS - 21
ER -