Assessing ion-exchange properties and purity of lipophilic electrolytes by potentiometry and spectrophotometry

Many ionic salts synthesized using metathesis are often found to contain significant amounts of impurities, despite careful control of the weighing of starting materials. In this work, a potentiometric method is devised to monitor ion-exchange properties (or 'purity') of an organic solvent...

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Main Authors: Silvester, Debbie, Grygolowicz-Pawlak, Ewa, Bakker, Eric
Format: Journal Article
Published: Elsevier 2010
Online Access:http://hdl.handle.net/20.500.11937/43875
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author Silvester, Debbie
Grygolowicz-Pawlak, Ewa
Bakker, Eric
author_facet Silvester, Debbie
Grygolowicz-Pawlak, Ewa
Bakker, Eric
author_sort Silvester, Debbie
building Curtin Institutional Repository
collection Online Access
description Many ionic salts synthesized using metathesis are often found to contain significant amounts of impurities, despite careful control of the weighing of starting materials. In this work, a potentiometric method is devised to monitor ion-exchange properties (or 'purity') of an organic solvent containing a lipophilic electrolyte. Its permselective behaviour is monitored by treating the solvent as a liquid membrane and contacting it with two aqueous solutions with different electrolyte activities. This electrolyte mismatch results in a drastic potential change when excess lipophilic cation-exchanger is titrated with anionexchanger, altering the membrane from being cation to anion responsive. Here, the cation-exchanger potassium tetrakis(4-chlorophenyl)borate (KTpClPB) dissolved in nitrobenzene was titrated with tetradodecylammonium chloride (TDDACl), in contact with Ag/AgCl electrodes placed in aqueous 1 M and 102 M KCl, respectively. The predicted potential change of 214 mV was observed at the equivalence point, forming the inert lipophilic electrolyte ETH 500, in a very small concentration range of added anion-exchanger (0.8% for 10 mV), suggesting good precision. The approach was confirmed by monitoring absorbance and fluorescence intensity changes of the chromoionophore Nile Blue. This method may be applied for the synthesis of a range of highly lipophilic salts for which established metathesis protocolsare not suitable.
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spelling curtin-20.500.11937-438752017-09-13T16:00:43Z Assessing ion-exchange properties and purity of lipophilic electrolytes by potentiometry and spectrophotometry Silvester, Debbie Grygolowicz-Pawlak, Ewa Bakker, Eric Many ionic salts synthesized using metathesis are often found to contain significant amounts of impurities, despite careful control of the weighing of starting materials. In this work, a potentiometric method is devised to monitor ion-exchange properties (or 'purity') of an organic solvent containing a lipophilic electrolyte. Its permselective behaviour is monitored by treating the solvent as a liquid membrane and contacting it with two aqueous solutions with different electrolyte activities. This electrolyte mismatch results in a drastic potential change when excess lipophilic cation-exchanger is titrated with anionexchanger, altering the membrane from being cation to anion responsive. Here, the cation-exchanger potassium tetrakis(4-chlorophenyl)borate (KTpClPB) dissolved in nitrobenzene was titrated with tetradodecylammonium chloride (TDDACl), in contact with Ag/AgCl electrodes placed in aqueous 1 M and 102 M KCl, respectively. The predicted potential change of 214 mV was observed at the equivalence point, forming the inert lipophilic electrolyte ETH 500, in a very small concentration range of added anion-exchanger (0.8% for 10 mV), suggesting good precision. The approach was confirmed by monitoring absorbance and fluorescence intensity changes of the chromoionophore Nile Blue. This method may be applied for the synthesis of a range of highly lipophilic salts for which established metathesis protocolsare not suitable. 2010 Journal Article http://hdl.handle.net/20.500.11937/43875 10.1016/j.elecom.2009.10.048 Elsevier fulltext
spellingShingle Silvester, Debbie
Grygolowicz-Pawlak, Ewa
Bakker, Eric
Assessing ion-exchange properties and purity of lipophilic electrolytes by potentiometry and spectrophotometry
title Assessing ion-exchange properties and purity of lipophilic electrolytes by potentiometry and spectrophotometry
title_full Assessing ion-exchange properties and purity of lipophilic electrolytes by potentiometry and spectrophotometry
title_fullStr Assessing ion-exchange properties and purity of lipophilic electrolytes by potentiometry and spectrophotometry
title_full_unstemmed Assessing ion-exchange properties and purity of lipophilic electrolytes by potentiometry and spectrophotometry
title_short Assessing ion-exchange properties and purity of lipophilic electrolytes by potentiometry and spectrophotometry
title_sort assessing ion-exchange properties and purity of lipophilic electrolytes by potentiometry and spectrophotometry
url http://hdl.handle.net/20.500.11937/43875