----- 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.

>  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. 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.

>  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: 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.
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.

>  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.

>
>
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