Ode Coyote wrote: > > > >Actually water is full of H+ and OH- radicals (10^-7 of water molecules in > >pure water will be disassociated), so the Ag+ has no problem associating > >with an OH radical, whether from disassociation of the water, or from the > >cathode. > > > >> > >> > >> Oxide Formation > >> ~~~~~~~~~~~~~~~ > >> When the ion concentration of both species is high enough, the > >> silver ions combine with the hydroxyl ions to form silver oxides. > > > >No, a hydroxyl has a hydrogen in it. When it combines with Ag+ it forms a > >hydroxide, not an oxide. > > > >Ag+ + OH- = AgOH > > > >That is the form that ionic silver is in from the point of being made. > > > >> > >> > >> There are at least two paths: > >> > >> Path #1: > >> > >> One silver ion combines with one hydroxyl ion to form silver > >> hydroxide: > >> > >> Ag(+) + OH(-) --> AgOH (silver hydroxide) > > ### OH radicals are conductive? > Conductivity drops over the first 24 hrs after making ionic CS and some > particles form in the meantime...possibly because there is 'some' dissolved > radical oxygen in the water that does what H2O2 does. > Could it be that we're making tiny amounts of H2O2 as the brew brews?
OH radicals are formed at the cathode. Normally these would repel each other, but at the surface where they are formed and the density is greatest I can see the possibility that some may join. If they do, then we would get H2O2. There are H2O2 test strips available, maybe we should try to get some and test for it. > > > Could it be that all the OH radicals have not yet associated with silver > ions at first, then if just a little H2O2 is added before they do all > associate, the radical oxygen atom on the H2O2 combines with the OH making > 2H2O...or just H2O and O2 and maybe free hydrogen that emulsifies in the > water for a time, then forms bubbles on the sides of the container... > releasing Ag particles? I don't see how you would get free hydrogen, it would be oxygen that is in excess supply. Beyond that, I don't know. The first thing we need to do is test for H2O2 in fresh brew and see if any is present, and if so at what level. > > > Could it be that the 'time' it takes for OH radicals to react is what's > responsible for the famed "stabilization period"? There is something happening during the stabilization period. There are several possibilities I can see. AgOH + AgOH -> 2Ag + H2O + O or -> 2Ag + H2O2 or -> Ag2O + H2O I think the kinetics most likely favors the last one. However the first one produces an O, which could then combine with H2O producing H2O2. So in the last case what would be happening is that some of the silver hydroxide is forming silver oxide. Since there will be half as many ions when in solution, the conductivity would drop aprroximately in half. The question is, does the conductivity ever drop by more than 50%. If so, this this alone could not account for it. If the first one is happening, then the conductivity could drop by more than 50%, and tyndall should increase. If the second one is happening it is hard to say what should happen, since H2O2 is a known wild card that could break down large particles at the same time it is forming new particles. > > > It's obvious that adding H2O2 to a very freshly done batch has a major > [and very fast] effect that appears to be identical in the end [but without > the gas bubbles..or at least no noticeable ones] to using current > controlled reversing polarity pulses at a specific frequency to produce > colorless particles at the outer boundaries while conductivity rise is very > much slowed and doesn't drop much later on. That would be the expected result if both adding H2O2 and stabilization are producing Ag2O, or as you point out, small amounts of H2O2 are generated during electrolysis that then does the same thing as adding H2O2, but over a longer period of time. I am going to try to find some hydrogen peroxide test strips, so maybe we can figure out some of this. The only fly in the ointment is that from reports, stabilization results in a drop in effectiveness, but adding H2O2 results in an increase in effectiveness. However, H2O2 is a very good germicide itself, so much or all of the effectiveness increase could be from the H2O2 itself and not from it's actions on the EIS. > > Adjusting pulse frequency adjusts zone concentrations while everything is > being emmitted at both electrodes into that zone rather than one or the other. > It's a cool effect that makes a very strong TE in colorless CS, but I > could rarely get everything balanced "reliably" to maximize the effect > repeatably. This is the first I recall having heard this discussed. Is it pulsed DC, or AC? What are the typical parameters of a setup such as this? > > > Further, Adding a single drop of H2O2 to a pint brewed with straight DC, > at the right time, appears to eliminate all the white electrode crud that > may have fallen off into the water. [No sparklies or anything settling > out..just a very fine dense TE corresponding with a huge fast conductivity > drop from around 20 uS to 6 uS. That is a surprising drop. It means that more than converting 2AgOH to Ag2O is happening, since that should only allow a 2:1 drop. Most likely it the following is happening, and you are getting both very small Ag2 particles and Ag2O in solution. 2AgOH + H2O2 -> 2Ag + 2H2O + O2 2Ag + H2O2 -> Ag2O + H2O Ag2O + H2O2 -> 2Ag + H2O + O2 Kinetics would define the ratio of Ag2O to 2Ag in the final mix of 2Ag and Ag2O population. > The TE becomes somewhat dimminished as > large gas bubbles form on the sides of the container indicating that part > of the initial TE was due to an emulsion of gas bubbles and water..not > certain "what" gasses.] I disagree with this assessment. I believe gas is the liberated oxygen, which dissolves initially, then slowly degasses on the surface and sides of the container. > > > Next test was to make a batch stopping at 20 uS, split it, add a single > drop of H2O2 to one still being stirred with magnetically coupled stirrer. > One stays crystal clear with medium strong final TE [virtually no initial > TE] and drops to 12 uS after 24 hours. [Typically 12 PPM at around 15% > particulate] > The other makes an instant extremely strong TE, instantly drops to 6 uS > and stays there. [Still 12 PPM but 65% particulate?] I believe both of these are explained by the above equations. The one sitting and aging is slowly converting to AgO, and the one that the peroxide was added to converted to both AgO and 2Ag particles very quickly. The first drops by about half, since there will only be about half as many Ag2O ions in solution as there were AgOH ions, and the second drops by a factor of 4 because of that, plus half or so of the Ag2O converts to 2Ag which has little effect on conductivity, so the end result is about 1/4 as many Ag2O ions in solution as there were AgOH. > > > Adding H202 to a colorless batch at 10 to 20 uS that's over 24 hours old > doesn't appear to do anything at all. That is odd, I would expect it to drop it by about 50% by converting Ag2O to 2Ag particles. Then again, the balance may be just right after aging so that although Ag2O is being converted to particles, the original particles that are present are converting back to Ag2O, resulting in a break even. The solubility limit of 13 ppm may also play into this as well. It would take some tests with a scanning photo spectrometer to determine what is happening to the particles. I will try to get mine set up again this weekend and make some tests. > > > BTW Once water is removed from ionic CS, the ions form some form of > silver oxide that water added later apparently won't touch. OK. There are a number of silver oxides, Ag2O, AgO, Ag2O2 and Ag4O4. Be aware that Ag2O has limited solubility, 13 ppm in cold water, so you have to add a lot of water to dissolve it back. All the other oxides are insoluble. What is the color? Ag2O should be brownish, the others gray or black. > > So, if oxides are being dissolved in the water, they must be different than > the kind that won't dissolve back into the water very well and different > from the oxides that form on one of the electrodes that also don't dissolve > into the water. [There are 4 different possible oxides...maybe 5] There are a number of oxides. Try lots of hot water with flushing, Ag2O is not easy to dissolve, but it will over time. The others should not dissolve no matter how hot the water or long the time. But I think you wil find they dissolve quickly in H2O2 from my experience. > > > To my way of thinking [speculation] one of these more soluable oxides > might form a nucleus around which Ag particles crystalize into larger > particles that display the various colors much like a snowflake [ice > crystal] will form around a dust particle in the air. Maybe, it is hard to say. But just a silver atom or pair should be sufficient for the snowflake type plating out to occur. If you look at photograpy development process, the silver grains grow on silver atoms or particles, not silver compounds. They start as compounds then plate out on the silver grains. I think this is applicable. > > Since H2O2 will destroy some types of oxides, that could be why adding > H2O2 to a batch of colored CS breaks up the crystals into colorless sizes. H2O2 reacts with silver metal producing silver oxide. This is easy to prove by taking some silver wire, and putting it into some 3% H2O2. Leave it a couple of days, and you will find that the metal will have a tan coating, similar to the cathode of an EIS setup, and also if you leave it long enough, a tan precipitate will settle to the bottom as the Ag2O exceeds the 13 ppm solubility limit of silver oxide in the water. > > A snowflake has radial arms extending from the center with inherent > fracture planes. > Using the 'As above, So below' axiom, if a nucleus is destroyed, it stands > to reason that the crystal will disinigrate along those fracture lines and > the resulting particles won't get any smaller than that, but still small > enough to stop displaying the color. [It's still size rather than oxide > that's responsible for color..but oxide responsible for size.] I am not saying this cannot happen, but applying Occam's razor, the simplest explanation is the simply oxidation of the silver in the silver particles. > > Various contaminants could also serve as that nucleus, explaining why some > 'bad' water ..even with a low conductivity...makes yellow CS while running > the same process in different water doesn't. Or if the current is not limited, it could be due to the excessive initial current density. > > ...and why using very heavily ozonated water tends to make yellow CS, but > using the same water in the same process after gas bubbles have formed on > the sides of the water jug, proving that something gaseous was dissolved in > it [assumed to be ozone due to what the label says, ie "ozonated"]...doesn't. > Ozonated water does not last long, the bubbles will be oxygen as the ozone combines to product plain old oxygen. > > > Assumption: High levels of dissolved ozone produces high levels of soluble > silver oxide which serves as a crystal formation nucleus broken up by the > later addition of hydrogen peroxide by destroying that nucleus. I agree with the first half of your assumption, but not necessarily the last half. However I cannot come up with a way to test this hypothesis. > > > Observation on another note: Adding a tablespoon or more of 3% peroxide to > quart of water, THEN running a batch, produces VERY large shiny snow flake > like silver particles in clear water that drop out and prevents > conductivity from rising past 13 uS even after running the batch for days > and days. Interesting, does not 13 uS equate approximately to 13 ppm of Ag2O, which is the solubility limit? My guess, when it hits 13 ppm, it becomes saturated and wants to plate out on something. In this case it is the particles of silver that are already there, and in something akin to photo developing, they actually reduce onto those particles add pure silver and evolving oxygen making them grow. H2O2 is a know photo developer, although rather poor, so I believe this makes perfect sense. > After sitting in sunlight for many months, the silver snowflakes > form black oxide balls on the bottom and the water goes yellow...still at > 13 uS. [What's with that?] That is the solubility limit of Ag2O, so that is not surprising, it simply means that there is an excess of Ag2O somewhere. Over time, as the H2O2 expires itself, it slowly converts the silver particles back to silver oxide, and silver oxide to 2Ag particles (and the sunlight causes some of the Ag2O to convert to Ag2 particles stuck together to form big black balls of silver power), that then plates out more silver, so over time the big particles get a silver oxide coating, and a silver powder coating, plus silver oxide in solution is forming new particles, that then grow to produce the yellow CS. The whole thing is very dynamic and ever changing as long as the H2O2 is present, and the result at any time depends on not only the concentration of H2O2, particles and Ag2O, but the temperature and exposure to sunlight. On top of that you have the developing power of H2O2 modulated by the ph, where a ph of over 7 enhances it, and below 7 inhibits it. > > It's apparent that "when" something is added, makes a big 'energy applied' > difference with respect to what happens. The starting point has a lot of influence on the resulting outcome, the butterfly effect so to speak. > > > Observations tend to bear out all the above assumptions and speculations, > but eyeballs [and meters] can be tricky. [Thinking it's #1 and/or #2 > doesn't eliminate the possibility of an un-thought of #3 and #4] Yep, unfortunately both silver and H2O2 are known to act in very strange ways, H2O2 oxidizing or reducing depending on other variables, and silver compounds being easily photo reduced, as well as easily developed or reduced with a number of different compounds acting as developers. > > > ..or, I see what I see, but what I think it is, isn't always completely [or > any part of] what it is. > ..but it sure seems like it. ;-) > > Being a broad generalist....a 'gee' whiz kid..a whack it with a hammer > from the school of knocks then see what it looks like type, I'm not all > that coversant in metallurgy and crystal lattice structures and the like, > but that's a little more along my fuzzy line than almost totally befuddling > electro chemistry. > > Can the chemically inclined whiz kids put it all together with the > metallurgical whiz kids? I think I have a pretty good idea what is going on. But some additional tests to support or disprove would be good. One thing I really want to know is if there is any H2O2 produced, and some strips should allow that to be determined quite easily. Marshall > > > Ode > > -- > No virus found in this outgoing message. > Checked by AVG Anti-Virus. > Version: 7.0.296 / Virus Database: 265.6.6 - Release Date: 12/28/2004 > > -- > The Silver List is a moderated forum for discussing Colloidal Silver. > > Instructions for unsubscribing are posted at: http://silverlist.org > > To post, address your message to: silver-list@eskimo.com > Silver List archive: http://escribe.com/health/thesilverlist/index.html > > Address Off-Topic messages to: silver-off-topic-l...@eskimo.com > OT Archive: http://escribe.com/health/silverofftopiclist/index.html > > List maintainer: Mike Devour <mdev...@eskimo.com>
