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Acidity of Frozen Electrolyte Solutions.

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Title: Acidity of Frozen Electrolyte Solutions.
Authors: Robinson, Carmen1,2 (AUTHOR), Boxe, C. S.1,2 (AUTHOR), Guzmán, M. I.1,2 (AUTHOR), Colussi, A. J.1,2 (AUTHOR) ajcoluss@caltech.edu, Hoffmann, M. R.2 (AUTHOR)
Source: Journal of Physical Chemistry B. 4/20/2006, Vol. 110 Issue 15, p7613-7616. 4p.
Abstract: Ice is selectively intolerant to impurities. A preponderance of implanted anions or cations generates electrical imbalances in ice grown from electrolyte solutions. Since the excess charges are ultimately neutralized via interfacial (H+/HO-) transport, the acidity of the unfrozen portion can change significantly and permanently. This insufficiently recognized phenomenon should critically affect rates and equilibria in frozen media. Here we report the effective 19F NMR chemical shift of 3-fluorobenzoic acid as in situ probe of the acidity of extensively frozen electrolyte solutions. The sign and magnitude of the acidity changes associated with freezing are largely determined by specific ion combinations, but depend also on solute concentration and/or the extent of supercooling. NaCl solutions become more basic, those of (NH4)2SO4 or Na2SO4 become more acidic, while solutions of the 2-(N-morpholino)ethanesulfonic acid zwitterion barely change their acidity upon freezing. We discuss how acidity scales based on solid-state NMR measurements could be used to assess the degree of ionization of weak acids and bases in frozen media. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Physical Chemistry B is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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An: 145138045
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  Data: Acidity of Frozen Electrolyte Solutions.
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  Data: <searchLink fieldCode="AR" term="%22Robinson%2C+Carmen%22">Robinson, Carmen</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Boxe%2C+C%2E+S%2E%22">Boxe, C. S.</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Guzmán%2C+M%2E+I%2E%22">Guzmán, M. I.</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Colussi%2C+A%2E+J%2E%22">Colussi, A. J.</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<i> ajcoluss@caltech.edu</i><br /><searchLink fieldCode="AR" term="%22Hoffmann%2C+M%2E+R%2E%22">Hoffmann, M. R.</searchLink><relatesTo>2</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+B%22">Journal of Physical Chemistry B</searchLink>. 4/20/2006, Vol. 110 Issue 15, p7613-7616. 4p.
– Name: Abstract
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  Group: Ab
  Data: Ice is selectively intolerant to impurities. A preponderance of implanted anions or cations generates electrical imbalances in ice grown from electrolyte solutions. Since the excess charges are ultimately neutralized via interfacial (H+/HO-) transport, the acidity of the unfrozen portion can change significantly and permanently. This insufficiently recognized phenomenon should critically affect rates and equilibria in frozen media. Here we report the effective 19F NMR chemical shift of 3-fluorobenzoic acid as in situ probe of the acidity of extensively frozen electrolyte solutions. The sign and magnitude of the acidity changes associated with freezing are largely determined by specific ion combinations, but depend also on solute concentration and/or the extent of supercooling. NaCl solutions become more basic, those of (NH4)2SO4 or Na2SO4 become more acidic, while solutions of the 2-(N-morpholino)ethanesulfonic acid zwitterion barely change their acidity upon freezing. We discuss how acidity scales based on solid-state NMR measurements could be used to assess the degree of ionization of weak acids and bases in frozen media. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
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  Group: Ab
  Data: <i>Copyright of Journal of Physical Chemistry B is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/jp061169n
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        Text: English
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              Text: 4/20/2006
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              Y: 2006
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