You will find Frank Key's previous response (rebuttal) at:
http://www.silver-colloids.com/misc/Ionic-response.htm
I will post the comments back to this forum, using that page as the original document. My comments are in BOLD::
1. Everything is soluble to some small extent, even a rock in water. The Chemical Handbook lists the solubility of AgCl to be 0.000089g/100 ml of pure water. This corresponds to 0.89 ppm, a small enough number for every analytical book in the world to list AgCl as insoluble.
Let's take a look at some real numbers. If we start with 5 ppm od EIS, that is 4 ppm of ionic silver, and take an ounce of it on a stomach that contains 3 ounces of liquid, then the result would be 1 ppm of ionic silver. Solubility of silver chloride is over 1 ppm at body temperature, so 100% of the ionic silver that is consumed would dissolve. I would not call that insoluble when dealing with concentrations of a few ppm.
2. AgCl does not dissolve inside the body:
Remember, solubility means the extent to which AgCl
forms Ag+ ions. In a chloride environment, the solubility
of AgCl would be less than it would be for pure water, a result which would
be expected from Le Chatelier’s Principle.
For the equilibrium
Ag+ + Cl- à AgCl (s)
Le Chatelier's Principle would state that the addition of chloride
would drive the equilibrium to the right, towards the insoluble AgCl side.
In a chloride environment, however, according to the Merck index, the amount
of Cl- in the bloodstream is about 3500 ppm, which translates to
approximately 0.1 M. Substituting this value into the above solubility
product equation, one calculates that the amount of ionic silver in the
blood cannot exceed 1.94 x 10-4 ppm. I definitely call that insoluble.
The bottom line is that ionic silver is not going to survive in a chloride
environment, but colloidal silver will
Your expert needs to go back to school. That equation is valid only for very low concentrations of Cl ions. For the blood, which is over .1 M it is not valid at all. Silver chloride at medium and higher concentrations of Cl ions forms complexes (AgCl2, AgCl3, AgCl4 etc.), which are very soluble. The correct equation for this is:
2X10^-10/[Cl] + 6.3X10^-7 + 3.4X10^-3[Cl]
where the [Cl] is the chlorine concentration in Moles, including the dissolved AgCl. This works out to very close to .9 ppm for blood (.145 Mole), which is coincidently almost exactly the same as it is in pure water. With higher concentrations of the chloride ion it is even higher. I have posted a graph from Ref #2 that shows this to a previous message to this newsgroup. For the concentrations we are concerned with, the left hand side "A" would be the applicable graph.
References for this are:
1. Forbes, Cole J. Am. Chem. Soc., 1921, 43, 2492. (This is volume
II of that years issues).
2. Laitinen "Chemical Analysis", 1975, second edition, pages 135-137.
http://www.sampleprep.duq.edu/dir/Chapter2/Chapter2.htm
http://genchem.chem.wisc.edu/demonstrations/Gen_Chem_Pages/15precippage/silverchloridedissolvesinxs.htm
http://www.ars-chemia.net/dr-milligans-classes/Classes/102/Notes/Solubility_Complex_Ions.pdf
http://iris.inc.bme.hu/en/subjects/inchem/sillabus/78-128.pdf
3. AgCl is eliminated by the kidneys, etc.
In the presence of ammonia, such as
from ammonium hydroxide, AgCl can be dissolved to form a soluble complex,
i.e.,
AgCl (s) + 2NH4OH -> Ag(NH3)2+(aq) +Cl- + 2H2O
but there is only about 0.2 to 0.8 ppm of ammonia in the blood, which
accounts for its slightly alkaline nature. The 3500
ppm of Cl- in the bloodstream is very far beyond the amount
necessary to prevent this from happening.
"Fulminating silver" ? This has nothing to do with ammonia.
A fulminate is an oxy-cyanide complex of a heavy metal. Let us hope
there is no cyanide in anyone's bloodstream.
A reducing agent will reduce silver ions to silver metal, but I cannot
imagine any set of circumstances which would cause ionic silver to be reduced
to the colloidal state.
The chlorine content does not prevent it from happening, it forms
an equilibrum such that there will be both species. But as
long as there is any of the complex present, then tollen's reaction should
be able to take place, and as the complex is used up, more of the silver
nitrate can convert to the complex even though the kinetics favors the
chloride.
The circumstance where ionic silver will reduce to the colloidal state are very well known in the photography business. All that is required is a developer, seed silver atom or particle, and a ph over 7. All can be present in the blood stream (caffine for instance makes a good developer). And if the silver is in the form of the ammonia complex, then it should reduce with glucose, which is also in the blood stream. See Tollen's reagent for more information on this.
As far as fulminating silver, once again your expert need to hit his books. Silver fulminate is an oxycyanide complex of silver, fulminating silver is formed when silver oxide complexes with ammonia. The formuleas are very different and I never discussed a fulminate at all:
Fulminating silver: A black crystalline substance, Ag2O.(NH3)2, obtained by dissolving silver oxide in aqua ammonia.
Silver fulminate, a white crystalline substance, Ag2C2N2O2, obtained by adding alcohol to a solution of silver nitrate;
But as you point out, with silver chloride what would likely be formed is neither of these, but Ag(NH3)2 (or AgNH3) instead. I am uncertain if that would participate in Tollen's reaction with glucose or not. But regardless, the dissolved silver chloride can still be reduced to silver particles through photographic development chemistry.
4. Argyria, etc.
I am not an expert on argyria, but if
argyria is caused by ionic silver in the bloodstream, I would think that
one would have to have more silver ions than chloride ions. By my
calculations, this would require drinking in excess of 5.5 g of silver
nitrate per liter of blood.
It is well documented that argyria can be acquired from silver nitrate
and silver citrate at dosages far lower than that. Rosemary Jacobs
got it from silver nitrate nose drops.
5. Particles vs. Ions
Of course ionic silver is more effective in preventing the spoiling of
milk. It is also more effective in treating surface (skin) abrasions.
The reason: THERE IS LITTLE OR NO CHLORIDE PRESENT. Once you
have chloride, the ionic will go to AgCl and only the colloid will be left
intact to kill the bacteria.
AgCl is still ionic when it is dissolved. The solubility is
about 1/15 that of silver hydroxide and silver oxide, but it is still ionic
when it dissolves.
Marshall
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