Unusual behavior of transport coefficients in aqueous solutions of zinc chloride at 25.degree.C

Weingaertner, Hermann; Mueller, Kathyrne; Hertz, H. G.; Edge, A. V. J.; Mills, R.

doi:10.1021/j150654a046

Cited by 58 publications

(46 citation statements)

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“…[28] and Lilich and Varshavsky [29] are distinctly less acidic than our solutions, Carriere et al's results [27] are much more acidic than ours, but Reiff s [26] are close. Lutfullah et al [23] reacted stoichiometric amounts of high purity ZnO and HC1, and Weingartner et al [17] reacted high purity Zn with HC1; their pH values are lower by 0.8 and about 1.9 pH units respectively. Attempts to add stoichiometric amounts of HC1 and Zn or ZnO thus seem to be very sensitive to minor concentration uncertainties.…”

Section: Methodsmentioning

confidence: 99%

“…Approximate Onsager transport coefficients for ZnCl2 [3,16] indicate it is an intermediate case; low concentrations are almost completely dissociated, whereas high concentrations are extensively associated. Further evidence for association includes the negative cation transference numbers above about 1.9 mol • dm"3 [16], Also, Zn and Cl tracer diffusion coefficients become nearly equal above 4 mol • dm-3, which indicates that anion and cation motions are highly correlated in these solutions [17].…”

Section: Introductionmentioning

confidence: 94%

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Mutual Diffusion Coefficients of ZnCl₂-H₂O at 298.15 K by Rayleigh Interferometry

Rard¹,

Miller²

1984

Zeitschrift Für Physikalische Chemie

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Zinc chloride / Aqueous solutions / Diffusion coefficientsVolume fixed mutual diffusion coefficients have been measured for aqueous ZnCl2 solutions from 0.005 to 5.652 mol • dm"3 at 298.15 K using free-diffusion Rayleigh interferometry. Most experiments were for stoichiometric high purity solutions, but solutions with either a 0.14% excess or several hundredths of a percent deficiency of HC1 were also investigated. These minor deviations from stoichiometry had no detectable effect on the diffusion coefficients; thus hydrolysis does not affect the results. The ZnCl2 diffusion coefficients exhibit a shoulder around 0.2 mol • dm"3 that may be due to selfcomplexing. Other workers have reported related anomalies in tracer diffusion coefficients of the H20, in viscosities, and in activity coefficient derivatives of ZnCl2 solutions.These anomalies appear to be characteristic of and limited to zinc halide solutions. Two commercial sources of ZnCl2 were found to contain large amounts of alkali metal and alkaline earth metal impurities; these impurities raise the diffusion coefficients but have little effect on the anomaly. Thermodynamic diffusion coefficients were calculated for ZnCl2 solutions and compared to similar data for other 2-1 chlorides; of the salts studied so far, ZnCl2 is unique with its double maxima. Wir haben mit Hilfe der Rayleigh-Interferometrie den Diffusionskoeffizienten fiir wiiBrige Zinklosungen (0,005 -5,652 mol • dm"3) bei 298,15 K gemessen. Die Mehrzahl der Experimente wurde mit reinen, stochiometrischen Losungen durchgefuhrt; in einigen Experimenten haben wir aber auch Losungen benutzt, in denen der Gehalt an HC1 entweder 0,14% oberhalb oder einige Hundertstel Prozent unterhalb der Stochiometrie lag. Diese kleinen Abweichungen von der Stochiometrie hatten keinen meBbaren EinfluB auf die Diffusionskoeffizienten, woraus zu schlieBen ist, daB die Hydrolyse die Ergebnisse nicht beeinfluBt. Die Diffusionskoeffizienten zeigen eine Schulter bei etwa 0,2 mol dm "3, die eine Folge von Komplexbildung sein mag. Andere Forscher haben verwandte Anomalien in Tracerdiffusionskoeffizienten, in Viskositiiten und in GroBen, die sich vom Aktivitatskoeffizienten ableiten, bei ZnCl2-L6sungen gefunden. Diese Anomalien scheinen charakteristisch fiir uns begrenzt auf Zinkhalid-Losungen zu sein. ZnCl2 von zwei kommerziellen Lieferanten enthielt groBe Mengen von Alkali-Metall-und AlkaliErdmetall-Unreinheiten. Diese Unreinheiten erhohen den Diffusionskoeffizienten, aber haben kaum einen EinfluB auf die oben genannte Anomalie. Wir haben die thermodynamischen Diffusionskoeffizienten fiir ZnCl2-L6sungen berechnet und sie mit ahnlichen Brought to you by | New York University Bobst Library Technical Servi Authenticated Download Date | 6/12/15 6:43 AM142 J. A. Rard and D. G. MillerDaten fur andere 2-1-Chloride verglichen; unter alien Salzen die bisher studiert wurden ist ZnCl2 mit seinem Doppel-maximum einmalig.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 94%

Mutual Diffusion Coefficients of ZnCl₂-H₂O at 298.15 K by Rayleigh Interferometry

Rard¹,

Miller²

1984

Zeitschrift Für Physikalische Chemie

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“…As was first pointed out by Weingärtner et al [37] and confirmed by Rard and Miller [7], the osmotic coefficients φ of ZnCl 2 (aq) at 298. Pitzer and Mayorga [48] noted that although ionic association is present in solutions of 2:2 electrolytes including divalent metal sulfates, re-dissociation is expected to occur at higher molalities because of the ionic strength variation of the activity coefficient factor.…”

Section: (Aq M)|agcl(s)|ag(cr)mentioning

confidence: 68%

“…The rather large variation in the values of that were attributed to the sudden onset of complex formation [7,[37][38][39], and that the Hittorf transport numbers for Zn(II) becoming negative above 2.0 mol·kg -1 was attributed to the formation of negatively changed zinc-chloro complexes [17,19]. There is more direct evidence for the nature of these complexes that will now be described.…”

Section: Znso 4 (Aq) Solutionsmentioning

confidence: 89%

Osmotic and Activity Coefficients of the {xZnCl2+(1−x)ZnSO4}(aq) System at 298.15 K

et al. 2007

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“…Earlier, the excess enthalpies of ethanol + water + ZnCl 2 have been reported by Zhao et al [15]. The transport coefficients in aqueous zinc chloride solution at 25°C have been studied by Weingartner et al [16]. Similarly, Banipal et al [17] have reported the volumetric studies of amino acids and zinc chloride in aqueous solutions.…”

Section: Introductionmentioning

confidence: 93%

Excess and deviation properties of {(glycylglycine+ZnCl2) in aqueous methanol} mixtures

Santosh

Bhat

2011

The Journal of Chemical Thermodynamics

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Unusual behavior of transport coefficients in aqueous solutions of zinc chloride at 25.degree.C

Cited by 58 publications

References 1 publication

Mutual Diffusion Coefficients of ZnCl₂-H₂O at 298.15 K by Rayleigh Interferometry

Mutual Diffusion Coefficients of ZnCl₂-H₂O at 298.15 K by Rayleigh Interferometry

Osmotic and Activity Coefficients of the {xZnCl2+(1−x)ZnSO4}(aq) System at 298.15 K

Excess and deviation properties of {(glycylglycine+ZnCl2) in aqueous methanol} mixtures

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Unusual behavior of transport coefficients in aqueous solutions of zinc chloride at 25.degree.C

Cited by 58 publications

References 1 publication

Mutual Diffusion Coefficients of ZnCl2-H2O at 298.15 K by Rayleigh Interferometry

Mutual Diffusion Coefficients of ZnCl2-H2O at 298.15 K by Rayleigh Interferometry

Osmotic and Activity Coefficients of the {xZnCl2+(1−x)ZnSO4}(aq) System at 298.15 K

Excess and deviation properties of {(glycylglycine+ZnCl2) in aqueous methanol} mixtures

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Mutual Diffusion Coefficients of ZnCl₂-H₂O at 298.15 K by Rayleigh Interferometry

Mutual Diffusion Coefficients of ZnCl₂-H₂O at 298.15 K by Rayleigh Interferometry