Nonaqueous Silver Nitrate Solutions. Spectral Studies in Acetonitrile

Baddiel, C. B.; Tait, M. J.; Janz, George J.

doi:10.1021/j100894a068

Cited by 31 publications

(8 citation statements)

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“…Several factors may cause this difference. One is that silver ion is known to interact specifically with acetonitrile, as is indicated by the fact that the standard reduction potential is about 0.16 V lower in acetonitrile than in water (see next section), and as is shown by the formation of silver-acetonitrile complexes (8, 21,22). Another factor is that the presence of a small ion in water decreases ordering by disrupting the high degree of structure normally present.…”

Section: Resultsmentioning

confidence: 99%

Silver-silver nitrate couple as reference electrode in acetonitrile

Kratochvil¹,

Lorah²,

Garber³

1969

Anal. Chem.

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Data as in Figure 11 exchange reaction at a membrane permeable to the exchanging ions, Rg in fact represents the sum of two resistances in series, one related to the kinetics of the ion exchange reaction and the second representing the mobility of the counter ions in the membrane. Where the glass membrane is coated by a surface-hydrolyzed film, the equivalent circuit has, in addition to that described above, a series Warburg diffusional impedance shunted by a resistance. It is, perhaps, surprising that under an applied electric field the counter ions show any diffusion at all as they are the major charge carrier present in solution. The large resistance in parallel with the Warburg impedance is interpreted as representing the effects of electromigration through 'pores' in the surface film.The results of the current step measurements of potentialtime curves are compatible with the equivalent circuit model obtained by impedance measurements. In the absence of a

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Section: Resultsmentioning

confidence: 99%

Silver-silver nitrate couple as reference electrode in acetonitrile

Kratochvil¹,

Lorah²,

Garber³

1969

Anal. Chem.

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“…Spectroscopic evidence for cation–π interactions in various organic solvents and in the gas or solid phase has been widely reported in the literature over the past several decades (e.g., Baddiel et al, 1965; Sunner et al, 1981; Munakata et al, 2000; Gokel et al, 2001 and references therein). However, spectroscopic evidence for cation–π interactions in aqueous solution has been extremely limited.…”

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confidence: 99%

Characterization of Cation–π Interactions in Aqueous Solution Using Deuterium Nuclear Magnetic Resonance Spectroscopy

et al. 2004

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Chemical interactions of aromatic organic contaminants control their fate, transport, and toxicity in the environment. Recent molecular modeling studies have suggested that strong interactions can occur between the pi electrons of aromatic molecules and metal cations in aqueous solutions and/or on mineral surfaces, and that such interactions may be important in some environmental systems. However, spectroscopic evidence for these so-called cation-pi interactions has been extremely limited to date. In this paper, cation-pi interactions in aqueous salt solutions were characterized via 2H nuclear magnetic resonance (NMR) spin-lattice relaxation times (T1) and calculations of molecular correlation times (tau(c)) for a series of perdeuterated (d6-benzene) benzene-cation complexes. The T1 values for d6-benzene decreased with increasing concentrations of LiCl, NaCl, KCl, RbCl, CsCl, and AgNO3, with the largest effects observed in the AgNO3 and CsCl solutions. Upon normalizing tau(c) values by solution viscosity effects, an overall affinity trend of Ag+ >> Cs+ > K+ > Rb+ > Na+ > Li+ was derived for the d6-benzene-cation complexes. The ability of Ag+ to complex d6-benzene was significantly reduced upon addition of NH3, which strongly coordinates Ag+ at high pH. Results with d6-benzene, d8-naphthalene, d2-dichloromethane, and d12-cyclohexane in 0.1 M methanolic salt solutions confirmed that spin-lattice relaxation rates are characterizing cation-pi interactions. The relatively strong cation-pi bonding observed between Ag+ and aromatic hydrocarbons probably results from covalent interactions between the aromatic pi electrons and the d orbitals of Ag+, in addition to the normal electrostatic interaction.

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“…For AgN03 in CH3CN, such studies by the Raman, infrared, and nmr techniques (up to 9.0 M AgN03) have been given in detail elsewhere. 14 It is sufficient for the present discussion to note that the salient spectral results confirm both the presence of ion pairs and pronounced solvation interactions; the complex species [Ag+(CH3CN)2N03-] becomes increasingly dominant at higher concentrar tions, with the disappearance of CH3CN as free or "unbound" solvent at mole fractions for AgN03 of 0.3 and greater. Recently, a crystalline substrate of the above 2:1 stoichiometry (mp 8°) has been separated from these solutions.20 It is thus of interest to examine the diffusion data of the present investigation for a possible correlation with the preceding observations.…”

Section: T H I S C O N T E N T Imentioning

confidence: 65%

Nonaqueous Silver Nitrate Solutions. Diffusion Studies in CH₃CN and C₆H₅CN

Janz¹,

Lakshminarayanan²,

Klotzkin³

1966

J. Phys. Chem.

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The diffusion coefficients for AgN03 at 25", by Stokes' diaphragm technique, are reported for concentrations from 0.1 to 5.0 M in CHaCN (E, 36.01; TO, 0.3413) and from 0.1 to 2.0 M in CsH5CN (E, 25.20; to, 1.211). The results are examined relative to aqueous diffusion data and relative to conductance, viscosity, and spectral studies in these nonaqueous solvents. A model is advanced in terms of a solvated kinetic unit to account for the character of the diffusive flow in these nonaqueous solutions. IntroductionIn recent years, transport properties of electrolytes in nonaqueous media have received considerable attention. While conductance and viscosity data are relatively abundant in the dilute region, diffusion results are apparently nonexistent for simple inorganic electrolytes in anhydrous organic solvents. The present communication discusses the application of the Stokes stirred diaphragm cell diffusion technique for nonaqueous electrolytes. First results for AgN03 in CH3-CN (to 5.0 M ) and in CeH5CN (to 2.0 M ) are reported, and the data are examined relative to related studies for AgN03 as an electrolyte in these two solvents as well as in aqueous solutions.

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Nonaqueous Silver Nitrate Solutions. Spectral Studies in Acetonitrile

Cited by 31 publications

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Silver-silver nitrate couple as reference electrode in acetonitrile

Silver-silver nitrate couple as reference electrode in acetonitrile

Characterization of Cation–π Interactions in Aqueous Solution Using Deuterium Nuclear Magnetic Resonance Spectroscopy

Nonaqueous Silver Nitrate Solutions. Diffusion Studies in CH₃CN and C₆H₅CN

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Nonaqueous Silver Nitrate Solutions. Spectral Studies in Acetonitrile

Cited by 31 publications

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Silver-silver nitrate couple as reference electrode in acetonitrile

Silver-silver nitrate couple as reference electrode in acetonitrile

Characterization of Cation–π Interactions in Aqueous Solution Using Deuterium Nuclear Magnetic Resonance Spectroscopy

Nonaqueous Silver Nitrate Solutions. Diffusion Studies in CH3CN and C6H5CN

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Nonaqueous Silver Nitrate Solutions. Diffusion Studies in CH₃CN and C₆H₅CN