On Aug 26, 2007, at 11:00 AM, Edmund Storms wrote:
Hi Horace,
The reason the conduction of water is said to be caused by ions is
because pure water is essentially an insulator. In fact, the purity
of water is normally measured by measuring its conductivity. As for
the speed of ions, an individual ion moves only a very short
distance. This is like electron conduction in a metal. When the
field is changed, the whole electron collection or, in this case,
ion collection moves as a unit all at the same time
instantaneously, i.e. with a speed of light reaction time.
Yes, that's the conventional electrochemistry pablum that starts with
the idealized "field between parallel plates" and culminates in the
Nernst equation. It all works out just fine at a gross level, even
though the underpinning assumptions are blatantly false, at least in
many circumstances.
In my experiments I used small platinum electrodes, which are not
plate like, but rather point like. At an electrode separation of 1
m, or 5 m or 10 m the E field from those points nearly vanishes -
especially considering the potential drop is almost all across the 2
cell interfaces. No problem - the results are the ions all start
their motion in harmony at near light speed. This of course can't
happen if the ions were point charges as in the above model. The
ions are in 1/r^2 fields, so if you compute the force from the 10 V
source I used you'll see the accelerating force should (a) be
practically non-existent, and (b) drop off as the square of the cell
length, which is does not. If there actually were a chain of ions
magically suspended in space (like ball bearings hanging on strings
with spring lateral connections) between the electrodes the force
would have to be transmitted from one to the next in a chain reaction
wave like scenario which is dependent or particle mass. This doesn't
happen, at least not to a large extent - though I did actually see to
a small extent the momentum related kinds of traces I originally
expected, so it may actually be possible to do some kind of ion
spectroscopy using this method. So, in any event, the "E-field from
parallel plates" idealization is completely bogus. I think Bockris
must have realized all this when he said cell conduction in the
electrolyte away from the plates is principally due to diffusion and
not the E field.
Here's yet another reason the "E-field between electrodes"
explanation is bogus: the 10 m cell, consisting of Tygon tubing
filled with Li2SO4 solution, could be bent in all kinds of
configurations, without changing cell currents. Included in those
configurations is the case where the electrodes are back-to-back,
facing opposed directions, i.e. with the Tygon tubes making a big
circle, but initially departing in directions opposed to the bulk of
the direct E-field between the electrodes. At this point one is
tempted to give the "electrolyte dielectric field" explanation - as I
did. It was a wrong hypothesis too. In order for the dielectric
field explanation to match the results the E field has to decline
linearly with distance between points, not as the square of the
distance or some other nonlinear declining function. So this
explanation doesn't fit the 1 m, 5 m, 10 m cell situation at all.
Further, here again, is the problem of the chain reaction of
neighboring nuclei effect causing inertial delays proportional to the
nucleus or ion mass, and related resonance effects - i.e. sonic
effects, which clearly did not happen.
I eventually solved this problem, I think. The E field within the
electrolyte is transmitted by a purely quantum effect - transmission
by direct electron orbital-to-orbital pressure. It is a kind of
orbital electron sound, and it travels at about 1/10 c. It is the
*electron shells* that move initially, and jointly, not the nuclei.
The shells have less than 1/1000th the mass of the nuclei. They move
in unison by a quantum wave form carried pressure. Electron fugacity
is thus highly related to, intrinsic to, electrolyte conduction. As
charge is added to either end of the lattice, or even a pseudo
lattice consisting of electron shells in a liquid, the electron
lattice adjusts, and the nuclei are later eventually brought along
for the ride if the compression wave is one way in the nuclei's
locality.
Now, you might ask how does this form of wave transmission differ
from sound? Why does the nucleus momentum not come into play? The
answer I think is one of degree. The electron orbital compression
wave is readily carried at high speed provided the dislocation
distance applies no significant force on the nucleus. The nucleus is
located in the center of a cloud of charge. In the absence of an
external E field, when integrating the force from that symmetric
cloud of charge, the force on the nucleus comes out to zero. The
effective charge within and up close to the nucleus, which is that
charge that determines nucleus-shell forces at small shell
displacements, is normally very near zero. The rest of the charge
outside a small displacement radius is unseen by the nucleus because
it self-balances, it is symmetric. Therefore, a wave involving only
minor motions of the electron shell, but yet simultaneous motions of
the entire shell, require very little energy. However, a small
displacement of the entire set of shells in a large body gets the
nuclei accelerating a small amount all at once. Carrying a pulse
with a significant amount of energy and momentum, i.e. sound,
requires nuclear motion, and it is transmitted atom to atom by
nuclear motion, and thus is very slow to transmit, and is carried by
large magnitude phonons. The amount of charge involved in the
"center of charge displacement force" varies exponentially with the
size of the displacement.
A third electrode in an electrolytic can be thought of as two cells
in series, with one side of the third electrode being the cathode
to one cell and the other side being the anode to the other cell.
As a result, nothing special is created.
My point was simply that after inclusion of a third electrode the
potential drop across the interface is reduced for DC and not as much
for AC. This concept might be useful for figuring out where an
observed change in electrolysis efficiency might be coming from. An
increase in efficiency in a particular blend of temperature, AC
current, DC current, and frequencies may be "special" in the sense of
useful.
Horace Heffner
http://www.mtaonline.net/~hheffner/
