Thermodynamic properties of chloro-complexes of silver chloride in aqueous solution

Fritz, J. J.

doi:10.1007/bf00646296

Cited by 55 publications

(39 citation statements)

References 28 publications

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“…Even though the solubility of AgCl in pure water is very low, on the order of 10 μM, it increases as the Cl − content increases, reaching 6 mM in 5 M NaCl 29,30 at 25…”

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Analysis of Ag Corrosion Products

Lin

Frankel

Abbott

2013

J. Electrochem. Soc.

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The corrosion behavior of Ag in outdoor environments and in a salt spray chamber was investigated. The coulometric reduction technique was applied to identify various silver corrosion products including Ag 2 SO 4 and AgO. These corrosion products were observed on samples exposed in certain field environments. A plateau in the coulometric reduction curve associated with metastable hydrogen evolution was observed under conditions in which a considerable amount of Ag 2 S was formed and reduced. Soluble silver chloride complexes were the dominant corrosion product, instead of insoluble AgCl, when the chloride deposition rate was high enough. Under those conditions, the corrosion rate measured by coulometric reduction is lower than the actual corrosion rate. Ag particles formed on the surface during exposure to different environments. During exposure in a marine environment, photodecomposition of AgCl corrosion product resulted in the formation of Ag nanoparticles embedded in AgCl. Isolated Ag particles of a few micrometers in size formed during exposure in a salt spray chamber due to the high exchange current density for the Ag/Ag + reaction. Ag is used in electronics applications, utensils, and decorative arts. Its corrosion behavior in indoor environments 1-3 and in lab chambers containing sulfur 4-11 has been studied. Ag 2 S is the main corrosion product and the kinetics of its formation rate usually are linear. The sulfidation rate of Ag increases as the concentration of H 2 S and carbonyl sulfide increase. Both of them generate HS − on the Ag surface in the presence of water and then HS − reacts with Ag to result in sulfidation.12 Therefore, humidity is critical for Ag sulfidation. The sulfidation rate stays low as long as the relative humidity (RH) is less than 35% but it increases significantly as the RH increases up to 95%. 6Recently it was reported that the corrosion rate of other metals such as carbon steel or aluminum alloys correlates with the concentration of atmospheric chlorides as assessed by the amount of AgCl formed on Ag.13 Ag has been used as an atmospheric corrosion monitor to measure environmental corrosivity, 13 which has attracted attention to the corrosion behavior of Ag in the field. Some interesting and maybe unique aspects of Ag outdoor corrosion have been reported. However, the details of how Ag corrodes in the field are not yet clear.Previous research shows that AgCl and Ag 2 S are the two most common corrosion products in the field, with AgCl usually dominating [14][15][16] except near a volcano with high emission of H 2 S where Ag 2 S is dominant.17 This might result from a higher deposition rate of chloride outdoors and is different than indoor exposure of Ag where Ag 2 S is more dominant than AgCl.12 Surprisingly, no AgCl was observed on the surface of Ag after exposure in an ASTM B117 salt spray chamber.14 One reason for studying the corrosion behavior of Ag is to clarify this discrepancy in behavior between field exposure and a supposedly accelerated laboratory test. Enhancing the...

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“…Even though the solubility of AgCl in pure water is very low, on the order of 10 μM, it increases as the Cl − content increases, reaching 6 mM in 5 M NaCl 29,30 at 25…”

mentioning

confidence: 99%

“…The solubility curve in Figure 13 (generated from literature data 29,30 ) describes the relationship between AgCl solubility and NaCl concentration at 25…”

mentioning

confidence: 99%

Analysis of Ag Corrosion Products

Lin

Frankel

Abbott

2013

J. Electrochem. Soc.

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“…High concentration of chloride ions in solution promotes enhanced solubility of the AgCl ( K sp AgCl=1.8×10 −10 , at 25 °C) surface layer of the Ag, AgCl electrode, through the formation of chloro‐complex ions, AgCl 2 − , AgCl 3 2− and AgCl 4 3− 7, 8, 9 , , , …”

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confidence: 99%

Surface Changes at Platinized Platinum Based Hydrogen Gas Electrodes Following Use in Highly Saline Aqueous Solutions

et al. 2014

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Platinized platinum based hydrogen gas electrodes, Pt(Pt)|H2(g)|H+(aq), and silver‐silver chloride electrodes, Ag|AgCl|Cl− (aq), make up the Harned cell, without transfer, working in the potentiometric mode at Cl− concentrations and ionic strengths, I, below 0.1 mol kg−1, for assigning primary pH values to reference pH buffer solutions. This work reports on experiments performed at higher I and Cl− solutions up to 0.7 mol kg−1, aiming at addressing seawater conditions with results of equally high quality. In the course of measurements, the occasional occurrence of highly unstable potentials denoted electrode malfunction; Pt metal surfaces observed by SEM/EDS and XRD exhibit strong Ag and Cl peaks corresponding to the presence of AgCl crystals deposited at both surfaces.

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“…Comparing Figures 1 and 2 indicates that the adsorption behavior of tin(II) and zinc(II) into these two resins was similar, while the adsorption behavior of silver(I) was slightly different. Since AgCl3 2− is the predominant species of Ag(I) in 5 M HCl solution [21], the adsorption of tin(II), zinc(II) and silver(I) into these two resins might be represented as is the predominant species of Ag(I) in 5 M HCl solution [21], the adsorption of tin(II), zinc(II) and silver(I) into these two resins might be represented as…”

Section: Purification Of Silver(i) By Ion Exchangementioning

confidence: 99%

Separation of Ag(I) by Ion Exchange and Cementation from a Raffinate Containing Ag(I), Ni(II) and Zn(II) and Traces of Cu(II) and Sn(II)

2018

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Ion exchange and cementation experiments were done to separate silver(I) from a raffinate containing silver(I), nickel(II), and zinc(II) and small amounts of copper(II) and tin(II). The raffinate resulted from the recovery of gold(III), tin(II) and copper(II) by solvent extraction from a leaching solution of anode slime. Ion exchange with anionic resins was not effective in separating silver(I) because tin(II) and zinc(II) were selectively adsorbed into the anionic resins. It was possible to separate silver(I) by cementation with copper sheet. Treatment of the cemented silver with nitric acid solution increased the purity of silver(I) in the solution from 50.9% to 99.99%. Adjusting the pH of the AgNO 3 solution to higher than 6, followed by adding ascorbic acid as a reducing agent, led to the synthesis of silver particles with micron size.

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Thermodynamic properties of chloro-complexes of silver chloride in aqueous solution

Cited by 55 publications

References 28 publications

Analysis of Ag Corrosion Products

Analysis of Ag Corrosion Products

Surface Changes at Platinized Platinum Based Hydrogen Gas Electrodes Following Use in Highly Saline Aqueous Solutions

Separation of Ag(I) by Ion Exchange and Cementation from a Raffinate Containing Ag(I), Ni(II) and Zn(II) and Traces of Cu(II) and Sn(II)

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