At 06:32 PM 9/9/2010 -0700, you wrote:
Some questions about electrolysis if people can comment:
1. Some say H+ ions are coming off of the anode. If so, where do
they come from? And in the case it comes from a water molecule, where
does the leftover OH- go?
## The anion is OH[-] and what portion doesn't turn Ag [+] into AgOH stays
in the water
2. During the initial stages, when silver cations are coming off the
anode, if they exceed solubility locally (before many anions have had
enough time to reach the anode), do these ions form metallic
particles?
## Most of the particles are AgOH
Since free electrons don't exist in a liquid, the only way to make a
metallic particle is for Ag[+] to pick up and electron from a surface
interface between the water and a surface.
Three spots can contribute an electron and two involve surface tension to
capture them.
1] Where the water meets an electrode. [surface tension at the interface]
2] Where a bubble adheres to an electrode blocking the water [surface
tension at the interface]
3] The surface of the glass container [from capacitive effect, electrons
produced from ambient electromagnetic radiation] ..also note that if those
metallic particle are made and don't have the velocity to escape that
surface as they are made, they will bond there forming a mirror.
Other things happen to the Oxides and Hydroxides as they are exposed to
free electrons..possibly peroxides of both, bonding to the glass on
opposite sides of that mirror that H2O2 won't touch...Black spot/ mirror/
white spot...all very hard to remove.
If so, how is it that ions (mutually repulsive) can get
together like that?
## They don't
Is it really like a collision just overpowering
that resistance?
3. They say particles have a zeta potential (which is the case of CS
is negative).
## Zeta potential is a very weak force easily overcome with particle
velocity..high [ish] speed collisions.
I suppose particles are said to be "in suspension"? In
solution, there are many silver ions with positive charge. Are these
negatively charged particles and positively charged ions mutually
attracted?
## Different sorts of charges [??] A loose attraction vs a "bond" [See Ag
ions and water molecules]
Or are things "in suspension" in a different universe than
things "in solution"?
## Yup
4. At the cathode, one electron reacts with one water molecule to
form (H + OH-). Then the H becomes H2 and escapes, right?
## Some escapes as bubbles, some dissolves.
If the bubble surface tension is loaded up, it's too heavy to rise and pop,
transferring the load to the upper surface tension of the water. [silver slick]
Then it will sink, whereupon the H2 will gradually dissolve into the water
and release part of the load as a white particle stream identical to what
comes off an electrode as the surface tension area decreases with the
shrinking of the bubble, pushing particles out into the water that no
longer have room to be there.
But it's not all Ag because AgOH will also get stuck in a bubble surface if
it impacts the bubble at a high enough velocity as it's growing on an
electrode that holds it still enough to get hit....the *why* of keeping
stir speed down to limit "Grey Beard", forming when enough silver is stuck
in the interface to be semi conductive, forming another bubble on ITs
surface as water pressure keeps IT stuck down.
"Grey Beard" grows INTO the direction of the water flow on a round
electrode as the pressure from the flow sticks the bubbles on tighter..or
in eddies behind the edges of a flat electrode where water velocity is
higher but hits at an angle to the facing surface, blowing bubbles off.
5. The gray colored sludge on the cathode is metallic silver plating
out, right?
## Mostly AgOH [Silver Hydroxide] and some metallic silver.
But, what gets "plated on" won't come off...thus, isn't "sludge"..but may
contribute to a rough surface, not being plated on very evenly as it has to
go between all the sludge particles to get to an exposed part to plate on to.
Why does so little silver appear to occupy so much
volume? Is the sludge full of air bubbles, making it look like a lot?
## Yup. Actually, Hydrogen bubbles full of sludge and some metallic
silver stuck on the inner surface of the bubble...waiting for a transfer
ticket.
6. When there is excess silver hydroxide, why does silverhydroxide
want to convert to silveroxide? Wouldn't it want to agglomerate into
particles? Or is it a combination of both? What chemically happens
to make silver hydroxide become silver oxide?
## I think that Silver Oxide particles tend to nucleate AgOH particles into
a loose crystalline structure. [and yellow color, both from pigment AND
particle size light scattering ]
H2O2 destroys that form of silver oxide, breaking the crystals apart.
7. So ultimately, there is some metallic silver particles, silver
ions (as either silverhydroxide or silveroxide), and silver
"particles" of silver hydroxide or silver oxide? And I suppose there
are "inter-racial" particles, right? Like a particle that could have
some metallic silver, silverhydroxide, as well as silveroxide? Are
there actually any silver ions left just by themselves?
## If the silver ions weren't "protected" somehow, they would ALL
eventually become silver hydroxide, but they don't.
Could it be that they orient themselves according to the [-] charge
influence of the oxygen atoms of water molecules by attraction, without
forming a "bond" [AKA "Hydration" ?? ]
Imagine:
2 eightballs of Hydrogen [++] and a cueball Oxygen [- -]....nested into, 2
eightballs and a cueball....nested into, 2 eightballs and a
cueball....tucked into... [ Dielectric structure ? ]
If you drop a 4 ball ...Ag [+] ..with an unoccupied charge....into that,
what happens? .....a water cluster with Ag [+] in the middle?
[Dunno]
8. I think Marshall said the black char on the anode is silveroxide.
Was it originally silverhyroxide that turned to silveroxide?
## You never see any Oxygen bubbles.
AgO... It's made there and stays there unless the current is high enough to
toss Oxygen atoms off into the water faster than they can oxidize silver
ions at that surface interface, thus forming those AgO particles IN the
water as that mistakenly named "Golden ion Cloud"
If you have both a Golden cloud and a White cloud, they tend to arc
downwards towards each other with a space of "nothing" in between [silver ions]
Some sort of exchange is going on there. [that adding electrons changes]
If that nothing space contacts glass, you get a mirror as those ions pick
up electrons from the glass surface. Glass is both a capacitor and, due to
metallic impurities in the silicon, a solar panel. [albiet, not a very good
one ]
Using a plastic container might actually reduce the formation of metallic
silver.
..with fast-ish water velocity and an electron gun? Hummmm.
Imagine an inverted surface TV tube as the water container...and an "I Love
Lucy" program, or Robin Williams....[ Laughter, best meds......Imprinted
Silly Silver ? ]
How about Phil Silvers? [OK, so I'm OLD ]
Ode
Thanks,
~David
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