Solubility and complex formation equilibria of silver chloride in dimethyl sulfoxide-water mixtures

Synnott, John C.; Butler, James N.

doi:10.1021/j100725a049

Cited by 45 publications

(6 citation statements)

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“…(12) shows that no difference can arise between the two scales in the concentration range here employed. The validity of the Lkbye-Hiickel corrections, and especially the arbitrary choice of the ion size parameter seems to be justified by the fact that our experimental pKs value at 2 5 T , when corrected from I = 0.01 to I = 0.1 amounts to 10.27+0.02 which agrees with the value of 10.279f0.003 obtained by Synnott and Butler [2] in 0.1 M LiClO,.…”

Section: Resultssupporting

confidence: 79%

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Temperature Dependence of The Solubility and Complex Formation of Silver Chloride in Dimethyl Sulfoxide

Rumbaut¹,

Peeters²

1970

Bulletin des Soc Chimique

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The temperature dependence of the solubility product of AgCl in pure dimethyl sulfoxide in the range 25 to 70 "C has been investigated. Thermodynamic values at zero ionic strength are estimated. Formation constants for the AgCI2-complex, existing in excess chloride are also tabulated as a function of temperature. The entropy and enthalpy data thus obtained are discussed in terms of ionic solvation. 1NTRODUCTlONIn a previous paper [l], a preliminary study of the solubility and complex formation equilibria of silver halides in a DMSO-NH,NO, solution was reported. It has meanwhile been recognized that in NH,NO, media ion pairing could have considerable influence on the ionic equilibria present [2]. Therefore, in the present work, we obtained our potentiometric data without addition of any supporting electrolyte, the slight variations in ionic strength being compensated for by Debye-Huckel corrections. Moreover, accuracy was gained by a modified titration device and by increasing the number of experiments. EXPERI MENTAL PARTReagent grade DMSO was dried during several days upon molecular sieves (Linde 4A), and then distilled twice under reduced pressure in a nitrogen stream. This gas, of high purity, was carefully dried over sulfuric acid and molecular sieves.The titration cell was water-jacketed and thermostatted to 0.05 "C. The silver electrode was a platinum strip, electrolytically plated with silver metal. The reference electrode was also a silver plated platinum strip, submerged in a 0.01 M AgN0,-DMSO solution. A special model of salt bridge was employed, so as to eliminate virtually any AgNO, diffusion into the titration vessel. It was filled with 0.01 M AgN0,-DMSO solution. All parts of the system, except the microburet (5 ml, 0.002 ml precision) were thermostatted.Potentials were measured by means of a compensation device composed of a Leeds and Northrup potentiometer and a pH meter Radiometer PHM 22p, which was used as a zero indicator. The accuracy of the measured potentials was 0.1 mV.Silver nitrate of high purity was crystallized twice from water by addition of methanol, dried in vacuo at 50°C and stored under nitrogen.

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Section: Resultssupporting

confidence: 79%

“…The principal equilibria involved during titration of a AgN03-DMSO solution with LiCl are: Solid silver chloride precipitates until the first equivalence point ( u~,~) is reached. Then the solid dissolves, forming the complex AgC12-and the second equivalence point is reached (ue,*), after which equilibrium (2) persists.…”

Section: Theorymentioning

confidence: 99%

Temperature Dependence of The Solubility and Complex Formation of Silver Chloride in Dimethyl Sulfoxide

Rumbaut¹,

Peeters²

1970

Bulletin des Soc Chimique

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“…(1) -8; (2) -6; (3) -4; (4) -2; (5) 0; (6) +2; z = -1; ci/e0 = % log ßlog ß°-0.022 = 0.2981<7m ~0.0197qM2 (24) Therefore, if the above mentioned assumptions are valid, it follows that 2.3…”

Section: Comparison With Experimental Data and Discussionmentioning

confidence: 98%

Charge dependence of free energy of adsorption at the electrode-solution interface

Rampazzo¹

1974

J. Phys. Chem.

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Publication cost assisted by the Consiglio Nazionale delle Ricerche Adsorption isotherms in which polarization energy of adsorbed ions is taken into account are examined. Under some extrathermodynamic assumptions, the dependence of the isotherm parameters In ß and A upon the electrode coverage and charge density qM are evaluated. Whereas the zero-polarization assumption of Levine, Bell, and Calvert leads to a linear dependence of In ß on qM, a quadratic dependence appears in the extended theory as a natural consequence of electrostatic interactions. Experimental data on (BPh4) -ion adsorption are in reasonable agreement with the above analysis.

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“…Eight separate measurements were made at each composition and CJ ranged from 5 mV in the water-rich solutions to 10 mV in pure DMSO although at one composition (50 wt. x) it reached 15 mV. If it is assumed that these results are equal to the standard real potentials of transfer of Ag+, then they can be combined with data obtained [33][34][35] for the solubility product of AgCl in these mixtures in order to calculate the real potential of transfer of chloride ion. It is this quantity which is shown in fig.…”

Section: Dimethyl Sulrhoxide + Water Mixturesmentioning

confidence: 99%

The medium effect for single ionic species

Parsons¹,

Rubin²

1974

J. Chem. Soc., Faraday Trans. 1

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The relation of the " medium effect " or " solvent activity coefficient " to the directly measurable real free energy of transfer is discussed. Measurements of the latter quantity for solutions in aqueous solvents containing methanol, ethanol, dioxan, acetone, ethylene glycol, formamide or dimethyl sulphoxide are reported and discussed. The surface composition of the solvent mixture is accessible and this information can be used to set reasonable limits on the possible value of the " medium effect ". Thus it can be shown that some assignments of single ion medium effects based on oversimplified models of solvation are inadequate. The assignment based on the neglect of liquid junction potentials between solvents is often surprisingly good.

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Solubility and complex formation equilibria of silver chloride in dimethyl sulfoxide-water mixtures

Cited by 45 publications

References 0 publications

Temperature Dependence of The Solubility and Complex Formation of Silver Chloride in Dimethyl Sulfoxide

Temperature Dependence of The Solubility and Complex Formation of Silver Chloride in Dimethyl Sulfoxide

Charge dependence of free energy of adsorption at the electrode-solution interface

The medium effect for single ionic species

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