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2016
ACL
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L.Mercury, K.I.Shmulovich, I.Bergonzi, A.Canizarès, P.Simon, 'Growing Negative Pressure in Dissolved Solutes: Raman Monitoring of Solvent-Pulling Effect', J. Phys. Chem. C 120 7697-7704 (2016) doi:10.1021/acs.jpcc.6b01700
Negative pressure in liquids is both an experimental fact and a usually-neglected state of condensed matter. Using synthetic fluid inclusions, namely closed vacuoles fabricated inside one solid host by hydrothermal processes, a Raman study was performed to examine how a superheated solvent (under negative pressure) interacts with its dissolved solutes. As a result, this contribution not only illustrates this well-known tensile state, but also displays evidence that a stretched solvent is able to pull on its dissolved solutes and put them also under a stretched state. The dielectric continuum hypothesis may lead to expect a stretching effect in solutes similar to the solvent’s, but our measurements evidence a damping mechanical effect (growing with tension), most probably related to solvation shells. A practical consequence is to retrieve the (also experimentally known) super-solvent properties of superheated solutions, though with a more complex picture that commonly expected. Another direct consequence is to envision that the superheating extension of one aqueous solution is composition-related due to the solvation efficiency and the percentage of residual free solvent.
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