DETERMINATION OF TRANSFER ACTIVITY COEFFICIENTS USING EMF CELLS WITH LIQUID JUNCTION.
Item
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Title
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DETERMINATION OF TRANSFER ACTIVITY COEFFICIENTS USING EMF CELLS WITH LIQUID JUNCTION.
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Identifier
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AAI8023670
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identifier
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8023670
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Creator
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GOLDBERG, SIDNEY S.
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Contributor
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Orest Popovych
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Date
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1980
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemistry, Analytical
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Abstract
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Transfer activity coefficients, log (,m)(gamma)(,i), of sodium (Na('+)), hydrogen (H('+)), triisoamyl-n-butylammonium (TAB('+)), and picrate (Pi('-)) ions were evaluated using e.m.f. cells with liquid junction between pairs of the following dipolar aprotic solvents: acetonitrile, N,N-dimethylformamide, dimethylsulfoxide, and propylene carbonate. Solutions of tetraethylammonium perchlorate (Et(,4)NClO(,4)), tetraethylammonium picrate (Et(,4)NPi), and triisoamyl-n-butylammonium tetraphenylborate (TABBPh(,4)) were used as salt bridges in these cells. Values of log (,m)(gamma)(,i) were calculated values of the liquid-junction potential.;The liquid-junction potential, E(,j), in cells with junctions between two solvents was attributed to the transport of solvated ions across the solvent-solvent interface. Equations for the calculation of the E(,j) in cells with and without salt bridges were developed. The E(,j) was formally divided into E(,j) which accounts for terms due to the transport of ions across the interface and E(,j solvent), which accounts for contributions to the E(,j) due to the transport of solvent molecules across the interface.;E(,j solvent) was calculated independently for two different cells with a junction between the same solutions but with different pairs of indicator electrodes. E(,j solvent) values between aqueous and methanol-water solvents were found to increase with increasing methanol content and showed an inverse dependence on the concentration of the current-carrying species in solution. Values of E(,j solvent) were lowered by the addition of saturated aqueous KCl salt bridges between the solutions studied. In addition, literature data of measurements of pH-cells with liquid junction in methanol-water and ethanol-water media were interpreted.
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Type
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dissertation
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Source
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PQT Legacy CUNY.xlsx
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degree
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Ph.D.
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Program
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Chemistry
