Conductance of Solutions of Alkali-Metal Halides in Glycerol

Hammadi, A.; Champeney, D. C.

doi:10.1021/je000044n

Cited by 10 publications

(12 citation statements)

References 13 publications

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“…In addition, it was reported by Kosuke [10] that the large negative E S values for NaCl and LiCl suggest structure-forming effects that tend to stabilize ion pairs, whereas the small negative value for KCl suggests a structurebreaking effect that tends to destabilize the ion pair. These findings are in qualitative agreement with previous results obtained for viscosity B coefficients of singly charged electrolytes dissolved in glycerol [18].…”

Section: Solvation Energy Of Ion Pairssupporting

confidence: 93%

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Ionic mobility and ionic association of singly charged ions in glycerol

Kameche¹,

Bouamrane²,

Blanco³

2005

Molecular Physics

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Experimental molar conductivity data for KCl, NaCl and LiCl in glycerol at 298.15 K were analysed by least-square fitting in the concentration range 0.5-100 mol m À3 in order to compute the values of the molar conductivity at infinite dilution Ã 0 and the Onsager constant S. Using previously measured transference numbers and assuming the Kohlrausch infinite dilution law, the limiting ionic mobilities were deduced. The results obtained show that the transport mechanisms in this solvent and other similar hydrogen-bonded solvents such as water and ethylene glycol are the same. The data were also interpreted in terms of ion-ion and ion-solvent interactions using the Fuoss paired ion model in the concentration range 0.5-100 mol m À3 . The fitting of Fuoss' equation of 1978 to these data led us to an estimate of the ionic association by computing the conductimetric pairing constants. The latter were further analysed by Gilkerson's equation to yield the difference between the solvation energy of the free ions and the ion pairs. The computed values allow an estimation of whether the electrolyte is a structure maker or a structure breaker.

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Section: Solvation Energy Of Ion Pairssupporting

confidence: 93%

“…The values for NaCl and KCl are in close agreement with those reported recently by Hammadi and Champeney [18] (Ã 0 NaCl ¼ 29:94 m À1 m 2 mol À1 and Ã 0 KCl ¼ 33:54 m À1 m 2 mol À1 ). The scatter in these values presumably reflects differences in the purity of the glycerol used.…”

Section: Debye-huckel-onsager Limiting Lawsupporting

confidence: 91%

Ionic mobility and ionic association of singly charged ions in glycerol

Kameche¹,

Bouamrane²,

Blanco³

2005

Molecular Physics

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“…We find below that HCl is less soluble in glycerol (K HCl (gly) ≈ 2 × 10 3 M 2 atm -1 ) than in water and dissolves less exothermically (∆H°H Cl (gly) ≈ -67 kJ mol -1 ). As in water and in ethylene glycol, H + diffuses much faster than does Clin glycerol, 14,15 suggesting that H + moves by shuttling along hydrogen-bonded glycerol chains. At high temperatures, HCl and HBr may react directly with glycerol to produce halohydrins such as XCH 2 CH(OH)CH 2 OH, 1 but we could not detect these products in our 294 K experiments.…”

Section: Introductionmentioning

confidence: 99%

Collisions of HCl, DCl, and HBr with Liquid Glycerol: Gas Uptake, D → H Exchange, and Solution Thermodynamics

2002

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Gas−liquid scattering, D → H exchange, and time-dependent uptake measurements are used to follow HCl, DCl, and HBr as they strike the surface of the neutral, hydrogen-bonding liquid glycerol. In this and the following paper, we report studies of gas−liquid energy transfer and trapping, the nature of HCl and HBr interfacial and bulk phase dissociation and recombination, and the thermodynamics of HCl solvation. We find that most HCl and HBr molecules readily dissipate their excess kinetic energy and thermalize at the surface of glycerol, even at impact energies up to 100 kJ mol-1 and glancing angles of incidence up to 60°. Nearly all thermally accommodated HBr molecules dissolve in glycerol for longer than 10 s. HCl is less acidic and dissolves reversibly for times of 0.1 to 1 s at incident HCl fluxes of (2 to 0.2) × 1015 cm-2 s-1, respectively. Experiments utilizing DCl show that this reversible solvation is accompanied by dissociation into D+ and Cl-, D+ → H+ exchange, and HCl desorption. The residence times of HCl in glycerol and their temperature dependences yield = −19 ± 2 kJ mol-1, = −67 ± 4 kJ mol-1, and = −165 ± 20 J mol-1 K-1 for HCl(g) ⇌ H+(gly) + Cl-(gly) at 294 K.

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“…[23][24][25][26] On the basis of our glycerol vapor pressure measurements presented below and in ref 17, we can extract the ion activity coefficients f ( of the NaI solutions via the Gibbs-Duhem relation. 27 The values listed in Table 1 and graphed in ref 17 follow the same trends as in water, initially decreasing with NaI concentration due to ion-counterion attraction 26 and, starting at ∼1 M NaI, increasing with added salt.…”

Section: Bulk and Interfacial Properties Of The Nai And Cai 2 Glyceromentioning

confidence: 99%

The Roles of Salt Concentration and Cation Charge in Collisions of Ar and DCl with Salty Glycerol Solutions of NaI and CaI₂

2008

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Gas-liquid scattering experiments are used to investigate the roles of ion concentration and ion charge in reactions of DCl with glycerol containing dissolved NaI and CaI 2 . Previous studies show that DCl molecules follow one of three pathways upon adsorption at the surface of pure glycerol: immediate desorption of DCl back into the gas phase, near-interfacial DCl f HCl exchange, and longtime solvation and dissociation. The electrolytes NaI and CaI 2 enhance immediate DCl desorption and D f H exchange at the expense of bulk solvation. We find that these enhancements rise linearly from 1.2 to 3.9 M NaI (5.5 to 1.4 glycerol molecules per ion), suggesting that the limited solvation of Na + and I -and greater ion-ion association at higher concentrations do not abruptly change or reverse trends in these pathways. DCl desorption and D f H exchange are equally enhanced by 0.7 M CaI 2 and 1.2 M NaI (nearly equal I -concentrations), but 1.3 M CaI 2 is twice as effective as 2.6 M NaI. This departure may be driven by the closer proximity of Ca 2+ to the surface at higher ion concentrations, especially if ion pairing between Ca 2+ and surface-active I -drags the cation toward the interfacial region. Argon atom scattering and surface tension measurements provide independent evidence for the presence of ions at the surfaces of the salt solutions.

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Conductance of Solutions of Alkali-Metal Halides in Glycerol

Cited by 10 publications

References 13 publications

Ionic mobility and ionic association of singly charged ions in glycerol

Ionic mobility and ionic association of singly charged ions in glycerol

Collisions of HCl, DCl, and HBr with Liquid Glycerol: Gas Uptake, D → H Exchange, and Solution Thermodynamics

The Roles of Salt Concentration and Cation Charge in Collisions of Ar and DCl with Salty Glycerol Solutions of NaI and CaI₂

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Conductance of Solutions of Alkali-Metal Halides in Glycerol

Cited by 10 publications

References 13 publications

Ionic mobility and ionic association of singly charged ions in glycerol

Ionic mobility and ionic association of singly charged ions in glycerol

Collisions of HCl, DCl, and HBr with Liquid Glycerol: Gas Uptake, D → H Exchange, and Solution Thermodynamics

The Roles of Salt Concentration and Cation Charge in Collisions of Ar and DCl with Salty Glycerol Solutions of NaI and CaI2

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Product

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The Roles of Salt Concentration and Cation Charge in Collisions of Ar and DCl with Salty Glycerol Solutions of NaI and CaI₂