In a message dated 11/28/00 4:48:58 AM EST, [email protected] writes: << Subj: Re: CS>Production of Silver Chloride at pH 2 Date: 11/28/00 4:48:58 AM EST From: [email protected] (Ivan Anderson) Reply-to: [email protected] To: [email protected] ----- Original Message ----- From: <[email protected]> > Roger, Perhaps not, but then that would make all such solubility > constants arbitrary, no? > > Ivan: I think you missed what I was saying: The Solubility Constant is NOT > arbitrary, it's the setting of [Ag+] = [Cl-] that is arbitrary. There is > probably no evidence behind THAT assumption. No, no, the concentration of dissolved AgCl only equals Ksp when the reactants are present in equal proportions. When the reactants are not present in equal proportions one reactant is dissolved in higher amounts than the other and the dissolved product AgCl is therefore equal to the concentration of the lesser dissolved reactant.
Ivan: Solubility Product is based on the assumption that there is SOLID CRYSTALINE AgCl present. Please go back and re-read the solubility product chapter in your inorganic chemistry book (If you think I'm wrong here, please quote from this reference showing that I have misstated the concept of ionic concentration with regard to solubility product ); In the case when SOLID CRYSTALINE AgCl is present, the [Ag] and [Cl] can be ANY concentration, BUT THE PRODUCT of these concentrations MUST equal the Ksp of AgCl WHEN SOLID CRYSTALINE AgCl is present. > Roger, with a fixed amount of silver, the concentration of the silver in > solution decreases to satisfy the Ksp constant in the face of rising > chloride concentration. > The solubility constant is the amount of dissolved salt (Ag+ and Cl- > discrete ions) in moles per litre of solvent, for equal amounts of the > component ions. > > Ivan: The solubility constant holds for any PRODUCT of [Ag+] X [Cl-] in > water. Equal concentrations of [Ag+] & [Cl-] are a special case brought about > when one STARTS with DW and ADDS XS AgCl crystals to it. In this PARTICULAR > case, the AgCl crystals dissociate in their components [Ag+], [Cl-] in equal > concentrations. Yes. > A concentration greater than the solubilty constant > results in that amount being precipitating as the molecular salt, AgCl > > Ivan: Here again, one must distinguish between a SOLID crystal AgCl and its > molecular, non-crystaline counterpart which, as I said before, probably does > not exist. However, in some cases it does. For example, I believe at very > high pH, UNDISSOCIATED MOLECULAR NH4OH exists. I am not exactly sure what you mean here, Roger. Ivan: I thought you were talking about UNDISSOCIATED, MOLECULAR AgCl dissolverd in water, and I was trying to point out that if we are talking about AgCl in terms of its solubility product, you should refer to it as crystaline AgCl to avoid any confusion. The dissolved amount of AgCl exists in concentration up to the solubility constant, and exists as discrete, free Ag+ and Cl- ions. Concentrations of these ions higher than Ksp combine to form the solid AgCl. In other words, if a teaspoon of the salt AgCl is stired into a litre of water a small amount will dissolve into Ag+ and Cl- ions and the rest remains a solid. Ivan: Exactly. Phew! > which, as you say, is a solid. The common ion effect states : that a > solute has a lower solubility in a solution containing one of its ions, > and is expounded in Le Chateliers principle. > > In general, the solubility of a salt containing the conjugate base of a > weak acid is increased by the addition of a stronger acid to the > solution. However, if the anion of a salt is the conjugate base of a > strong acid the salt is not soluble in the strong acid. > > The solubility of AgCl is unaffected by changes in pH because Cl - is > the anion of a strong acid and therefore has negligible basicity. > > Ivan: Thanks for this information. So your calculation at acidic pH is > probably correct for the case when you set the [Cl-] to the equivalent of pH2 > and calculate the [Ag+]. From your results it would appear that practically > ALL the ionic silver would have precipitated. Don't you think? Yes, all but about 0.01ppm is precipitated. Note, that this does not mean that the rest is not absorbed into the body in the small intestine. Ivan: Seems like awfully small potatoes, don't you think? > > Ivan: I still need you to explain to me how clusters of silver metal > > particles which have a net positive charge of one (as represented by > CS) will > > interact the way you have described above. I also need to know what is > > present in the stomach which will convert the bulk of the CS which is > in the > > form of neutral silver metal into INDIVIDUAL silver ions. Roger > > This is not the representation that I believe is typical of CS at all, > at least of LVDC CS. It is my contention that CS is the aggregation of > single atomic ions, it is ions that are emitted from the anode and these > form distinct crystal like structures of specific numbers and may even > be arranged in fractal patterns. Far from each particle (group of atomic > ions) having a single positive charge, it has the charge of the sum of > the ions incorporated (more or less). > > Ivan: If THAT were the case then explain what forces are present to hold > groups of 20 to 50 positively and INDIVIDUALLY charged ions in such close > proximity. In addition, are we to expect that much larger particles of say > 500 - 1000 silver atoms have this characteristic as well when we know from > experience that particles this large flocculate and eventually drop out of > suspension (presumably because there is a much weaker positive charge > associated with such particles)? Is there a much weaker positive charge that > hold larger particles apart. If there is, at what particle size is there a > transition and how is such a transition brought about? Van der Waals forces and other as yet not understood attractive forces. A colloid is a dynamic system of dispersive and attractive forces. Ivan: You still haven't explained what forces will push these INDIVIDUALLY charged silver ions together into a tiny little ball Most of the large particles found in LVDC CS are those that have formed dendrites on the cathode and have regained electrons, and which are then dislodged and re-enter the colloid. Ivan: So, in fact, these larger particles DO NOT HAVE INDIVIDUAL silver ions. Isn't that what you're saying? At what CS particle size does each silver ion within the particle begin to lose its individual charge? Why does this occur? Can you cite studies that provides evidence for this phenomenon? > If this were not so, then would any battery be able to be recharged? > > Ivan: Batteries operate on the principle that discrete ions carry the charge > from one electrode to another. IMHO, colloidal silver suspensions are > electrostatically charged whereby most of the silver exists as neutral atom > clusters, with each cluster having lost approximately a single electron. The > smaller the clusters the more highly charged and stabile the bulk of the CS. > I do not believe that individual silver ions are generated at the positive > electrode. Instead, clusters of ATOMS break off at weak points in the metal > lattice where the free energy of formation is slightly lower than at other > parts of the electrode where the silver has a more uniform lattice (i.e., no > missing atoms). Roger Roger, the electrolysis of silver is exactly comparible to the recharging of a battery, at least when done using low current densities. The only difference is that the electrolyte we use is water. By way of illustration, when I measure my CS with the my Ion Selective Electrode (ISE, which measures the activity of silver ions only) my results are within 2ppm of certified Atomic Absorption measurements (and mine are probably more accurate). Ivan. > >> -- The silver-list is a moderated forum for discussion of colloidal silver. To join or quit silver-list or silver-digest send an e-mail message to: [email protected] -or- [email protected] with the word subscribe or unsubscribe in the SUBJECT line. 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