From: medb@cc.newcastle.edu.au (Dieter Britz)
Subject: Re: Peroxide again!
Organization: University of Newcastle, AUSTRALIA
Date: Thu, 23 Jul 1992 23:56:11 GMT

In article <1992Jul23.043326.3736@ecsvax.uncecs.edu>, jrw@ecsvax.uncecs.edu
(James R. White) writes:
> In article <1992Jul22.210626.1@cc.newcastle.edu.au>
>  medb@cc.newcastle.edu.au (Dieter Britz) writes:
>> In article <1992Jul22.033005.14971@ecsvax.uncecs.edu>, jrw@ecsvax.uncecs.edu
>> (James R. White) writes:
>>>                ... The most likely chemical explanation is that
>>> deuterium peroxide (D2O2) is being formed at the platinum anode. ...
>>
>> We've been down that path, as our politicians like to say. Forget peroxide.
>> At the overpotentials in cnf electrolysis cells, you go straight to O2 at the
>> anode. ...
> 
> An overpotential of half a volt is enough to allow peroxide to form.
> This is an order of magnitude less than the total voltage at which
> many cnf cells operate, and the potpourri of contaminants that are
> present might well cause such an overpotential. This is a much less
> exotic assumption than that there is a radiation-free ash-free nuclear
> process producing the heat.
> 
> Do you know what the overpotential at the anode is in any of the cells
> which have produced large bursts of heat?
> 
> After considerable thought, I have concluded that the most impressive
> results must be due to either peroxide or something much more exotic.
> The amount of excess heat in these results is too large to be explained
> by calorimetry errors. And only deuterium and oxygen are present in
> large enough quantities to store the huge amount of energy involved.
> That is why I would like to see peroxide taken seriously, and decisively
> ruled out (or in) by the researchers who are getting these impressive
> results.

I think you have it the wrong way around. Electrolysis of water produces
oxygen at the anode; oxygen is the end of the road, while peroxide is part
way down the road of oxidation. So the larger the overpotential, the less
chance of getting peroxide. The actual overpotential achieved is hard to know;
FPH claimed 0.8 V but didn't say how they got that. Being an experienced
electrochemist, though, Fleischmann can probably be trusted with the figure. He
knows about such complications as iR drop (the total cell voltage is the sum of
the overpotentials at cathode and anode, and ohmic drop in the solution).

Jorge Stolfi emailed me privately and submits that Tom's gas loss is best
explained in terms of D2O2 formation. This could be tested by either taking
out an aliquot from the cell and testing chemically for peroxide (I think
iodide should do, but would want to look at a table of standard potentials
to be sure) - or to inject a drop of a test solution, something I am sure Tom
would shudder at the thought of.

In the next few days, I'll be posting a paper by Riley et al, in which they
describe in situ deuterium loading measurements using gas volume. They get
precisely what one expects, with one puzzling exception, where they get a
loading of 1 instead of about 0.75-0.8. This supports my contention that
peroxide can be forgotten about.

Dieter alias medb@cc.newcastle.edu.au
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