kirkshanahan
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Posts by kirkshanahan
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Thanks for the votes of confidence…
That being said I want to make my position clear. I have been looking at the CF field since 1995, resulting in 4 published journal articles and 1 whitepaper in the 2000-2012 timeframe. I have been paying less attention recently than in prior days, but I have not seen anything (at all!) that seems to be convincing evidence for CF or LENR or whatever you want to call it. What I do see is a bunch of researchers who have pre-concluded that LENR is the cause and who then force fit all results to that foregone conclusion. There have been a few half-hearted (I probably should have used another body part for a better description) attempts at addressing possible ‘mundane chemical’ causes of the observations, but none that are truly exclusive of chemical explanations. I also see lots of theories being developed with the pre-assumption that LENR is real. As such I ignore them because theories developed from bad data are bad theories.
Also, I do not have expertise in radiation monitoring, just basic knowledge, thus I have never commented on details of radiation measurements.
With respect to the ongoing experiments of MS then, I can offer chemical insight only. Some I have already done, but there are a couple more points to be made.
- LiOH is NOT a control for LiOD. H is NOT a control for D. There often but not always are significant isotope effects, and chemists expect H to behave differently from D. If you do LiOH/LiOD comparisons, do not neglect to fold in that expectation. (yes, that complicates.)
- Paper is a compounded substance. It has lots of pieces in it. Each comes with its own set of issues. One in particular regarding the observations of radiation signals is that paper uses fillers. Fillers are usually mined minerals, with a set of radioactive contaminants. Different papers, and even different batches of the same papers, can have differing contaminant levels. Manufacturers control what they must only, not everything.
- Water extracts contaminants from materials, and basic (LiOH) solutions can accelerate that. The paper used to cover the cells WILL BE wet, even if not apparent to the eye, since it may be surface absorbed on the paper components. So the paper should be independently tested. Run an experiment with warmed electrolyte in a standard cell, but where no electrolysis is ongoing. I would even push it, and heat the water to 75C or greater to maximize the vapor content. Keep going for as long as you would run an electrolysis run.
And finally, make sure you have no instrument artifacts. As Robert commented these can be significant. I recall Scott Little had a picture up on his Web site for a while where he showed a meter measuring something, and next to it a picture of the same meter after rotating it 90 degrees. It showed a different number. Likewise, I have previously mentioned the problem Ed Storms had with his Pt F&P cells, where he had a negative feedback in his equipment that gave a shift in baseline proportional to applied current. He had to redo his grounding to get rid of it, but his original setup was per manufacturer recommendations. Don’t trust vendor specs.
If I think of more later I will mention it.
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@MS...Some thoughts...
“extending even above the electrolyte. “
Might be due to splashing up of electrolyte…
“The Ni wire is now black,”
Some possibilities (from C&W again, pps 890-3):
NiO is a green solid, but on a wire surface could look black. Forms when hydroxide (deuteroxide) is heated (the description might be for solution, but should apply to solid surface also I would guess). (Also recall that long time at low heat can often slowly do what happens faster at higher T.) Ni hydroxide would form on the surface by reaction with LiOH(D). NiO dissolves readily in acids, so you might try a quick dip in some acid and rinse to see if that removes the color once you are done.
NiS is a black solid. I would worry that perhaps you are extracting (leaching) some sulfide from the paper cover. That would take a little time to build up enough S(2-) in solution, so the timing of the black color’s appearance might negate this possibility (if it happened very early in the run (Sorry I don’t recall the details of your run). You can get S from the air but I don’t know if you could get enough to do what you see. Lots of acid rain where you are?
Notice that these are not electrochemical reactions I am talking about, just normal ‘solution’ chemistry. Doesn’t mean there aren’t electrochemical reactions too though…
Edit: Found an interesting paper on determining reducible sulfur in paper. Very low concentrations found usually. Note comments on 'tarnishing', which is blackening of course: http://www.tappi.org/content/tag/sarg/t406.pdf
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BTW, if you are precipitating a lot of your electrolyte out, the cell resistance should be changing dramatically. As well, gelled precipitates like 'hydrous TiO2' might well impede conductivity I would guess.
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"The precipitates obtained on adding base (LiOD) to Ti(IV) solutions are best regarded as hydrous TiO2. This substance dissolves in concentrated alkali hydroxide (lithium deuteroxide, although your electrolyte may not be concentrated this much), to give solutions from which hydrated "titanates" having formulas such as M(I,2)TiO3.nH2O and M(I,2)Ti2O5,nH2O (possibly like Li2Ti2O3 or Li2Ti2O5) but of unknown structure may be obtained." (C&W, p. 810, my specific suggestions as to identities of compounds in parentheses)
Pure TiO2 is white. Impurities like Fe can color it however, often making it black. (An alternative to the black color J5 saw could be nanoparticulate Ti or TiD2, as adding hydrogen to H-absorbing metals causes swelling which leads to decrepitation (small particulates flaking off) in brittle materials.)
Ti would dissolve as ionic Ti(IV) due to base leaching of the typical Cl- contaminant in typical 'Ti sponge' to maintain charge balance. I examined several 'Ti sponges' many years ago (which are manufactured electrolytically using MgCl2 IIRC) and found the Cl- concentration of all of them to be in the several hundred ppm range. That also suggests the possibilities of Cl precipitates. Also IIRC, AgCl precipitates readily and is white. Any Ag present in your system?
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milky-white,
Sounds like 'hydrous TiO2' (Cotton and Wilkinson, Adv. Inor. Chem. 3rd ed., p.810-811.
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Responding to Jed's post from here: Atom-Ecology
JR: "Why would anyone doubt such results?"
Maybe because he says this in K. Cedzynska, S. C. Barrowes, H. E. Bergeson, L. C. Knight, F. G. Will, Fus. Tech. 20 (1991), 108-112
“Unfortunately, in evaluating the applicability of this analytical procedure for reliable tritium determination, we find the open-system technique to be sometimes subject to artificially high count rates (due to color effects in the solutions and, possibly, to metal contaminants in the palladium), and also to artificially low count rates (due to possible loss of gaseous tritium during the various steps involved in the open-system procedure.)
And this:
“It is much more likely [compared to the idea of T contamination from manufacture of Pd] that tritium contamination is introduced through improper handling of the metal or improper analytical procedures.
And this in K. Cedzynska, F. G. Will, Fus. Tech. 22 (1992) 156-159
“In a previous technical note [refs the 1991 paper quoted immediately above], we described the results of tritium analysis in palladium employing an open-system analytical procedure essentially identical to that used by Wolf [refs the transcript of a talk given at Stanford U. on 8/11/90]. …we concluded that this technique cannot be expected to yield reliable results.”
And
“We have developed…[a closed-system method]. This technique employs a [micro]distillation and catalytic gas recombination procedure…”
And
“The closed-system analytical procedure described here is not affected by the shortcomings of open-system techniques, such as falsely low or high tritium readings.”
Then add in the fact that I recall about zero tritium reports where the analytical method was clearly delineated. In the paper Jed quoted, Will says "The H2O and 0.5 M H2SO4 contained no measurable tritium within the accuracy of the liquid scintillation counting [29,30]". Refs 29 and 30 are the two papers I quote above. But which method did he use? Technically, if he believes his own work, he would use the 1992 method (ref 30) and forego ‘29’ (the 1991 ‘open’ method) totally. He does reference the closed 1992 method for the Pd analyses, but what about the electrolyte?
Will specifically says: After completing an experiment, which generally lasted for about a week, the electrolyte, Pd electrode and gas were analyzed for tritium and compared with the amounts of tritium present before the experiment. The Pd electrodes were cut into several pieces, of which four were analyzed individually.” which gives no information on how he analyzed the electrolyte.
Does he confirm that there are no problems with measuring T in the electrolyte as he found for measuring T in dissolved Pd solutions? No. He is *very* clear w. r. t. the Pd, but not with the electrolyte. The field of Pd CF is loaded with examples of surface contaminants on the electrodes. Where do those come from? Probably deposited from solution (at least some of them). Does that impact the T measurement like it can in the dissolved Pd cases? Unknown.
So even Will himself is skimping on the analytical method description, and by dual-references he leaves us wondering which he used. Most of the time, other CFers just say ‘we used LSC’ with no further comments. That’s like saying ‘we used calorimetry’. Totally inadequate description. Inadequate descriptions inspire no confidence. residual ambiguities inspire no confidence.
Secondarily, there's rarely any significant level of replication in the experiments, so we have the usual 'much claimed, little supported' situation with tritium analyses. From the paper Jed quoted (regarding prior T determinations) "Unfortunately, these findings are not generally reproducible or predictable," So that means you have to discount all the papers he references in his introduction to the paper (refs 1-25).
So in the field as a whole one has to ask: “Are there any reproduced and reproducible tritium measurements?” My answer to that right now is "No".
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Let's switch to actual work
Not trying to be adversarial here, just pointing out that:
A.) The F&P stuff is 'actual work'. In fact it essentially started the whole CF-LENR field.
B.) Nothing is stopping you from starting a thread on whatever you want.
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Oh please don't make me dig up your quotes again. It is too much of a pain
Expected begging off...everyone realizes that you claimed
Except that I and others have often dug up your messages.
So, supposedly you have already done this. Shouldn't be that hard to point to that perfect example where you quote what I said that you seem to think is so ridiculous. C'mon Jed, do it for the newbies reading here...
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You claimed this happened.
you also repeatedly claimed
Don't claim that I claimed. That's doing exactly what I said you do, put stuff together in your head and act as if it was true. Quote the quotes. If you can't, shut up.
Oh, and make sure you don't quote out of context, that is one of your favorite methods of mixing things up.
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Except that I and others have often dug up your messages. When we do that, you shut up for a while. Then you go and make the same claims again. Then after a while you deny you made the claims.
Actually JR, I am amazed at how much projecting you are doing. You sound like you are describing yourself.
For the record, your constant referral to the bucket evaporation mis-states the discussion I was adding to w.r.t. a parametric study of what it took as far as temp + air flow + surf area + humidity to get a bucket to evaporate overnight. As is your practice, you take words that are written by your designated enemies (i.e., anyone who disagrees with you or challenges your heroes) and assemble them together in new ways with the intent of denigrating the original writer, with no respect of what was originally said. Then you repeat your construct ad nauseum.
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Then please explain the (missing) huge chemical excess heat of the control...
Ummm...gosh that's so tuff....ummmm...no ATER so no CCS?
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Well, if they won't supply the data, you have no choice but to beat on them until they do.
Actually I did pretty much that 'back in the day'. As I recall, he would assert he had done CF and I would say 'then show the data'. As I said above he never did, primarily because he was working 'under the radar' and hadn't retired yet. Remind you of any current events...
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and they are easily disproved.
Perhaps, but we'll never know since no one who might be able to test them will even acknowledge I've made a legitimate criticism. But the facts as they stand today is that w.r.t. CCS/ATER no one has shown any significant defect in the theory/hypothesis/proposition/ supposition/whatever.
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though it is perhaps diffivult to get tight bounds in open cells.
The simple Two Zone Model applies in either case. Here are the primary differences:
In a closed cell, in order to avoid a pressure rupture (which would be most likely followed by a flash fire) there is a recombination catalyst in the gas space of the cell. This is missing in an open cell. Instead we have a vent port through which electrolysis gases, water vapor, and entrained liquid water/electrolyte exit the cell.
Both types of cell typically (not always) use basic electrolytes. This always dissolves a little bit of the Pt and Pd, which then can deposit in other places. This has been shown to be on the electrodes by surface studies of used electrodes. The dissolved metals, which are in ionic form, can also be splashed onto the sides of the cell in the gas space. There they can (not always) be metalized by reduction with hydrogen, which forms a 'nano'-sized metal particulate on the wall that is an excellent catalyst for recombination. In the closed cell, this will be very difficult to detect since the recombination at the metal particle has not moved to a different enough heat capture efficiency zone. However, in an open cell it should be easily detectable (given the usual detection limit considerations) by two methods: Loss of lost water volume and detection of the recombination heat. Said heat will be in the lower efficiency zone of the Two Zone model, but in fact it may well have another associated detection efficiency, since it is well removed from the major loss pathways represented by the penetrations through the cell top, so it may well be under measured. Details matter here,and the Two Zone Model is not sophisticated enough to quantify this well.
When ATER begins in an open cell, the recombination heat would be measured no differently from a closed cell, i.e. it is showing up in the high efficiency zone and will be inflated by 'old' (pre-ATER) calibration, giving an inaccurate apparent excess heat.
But I don't see any particular reason to believe the open cell case would be any less accurate than the closed cell if calibrated as I suggested with two heaters in the cell, one in the liquid and one in the gas. Always open to valid corrections of course.
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[written to THH] Your repeating "they didn't check" does not make it true.
ROFL
And your repeating over and over that I claimed such and such when I didn't doesn't make it true either!
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In Nagel's ICCF21 summary he talks about Staker's contribution. He (Staker) is a Loyola University Maryland prof who has been involved with LENR since 1989.
Mike Staker used to work at the Army Research Lab. He and I had a few go-rounds on sci.physics.fusion. He didn't like my propositions but never would supply any data to back up his claims. The story I got is that he was working 'under the radar' and didn't tell his management about it until he retired. I suppose he ended up at Loyola after that.
" post by Mike Staker who claims to have achieved a sustained fusion reaction in Pd in his lab At Army Research Lab? " - from post to spf by Tom Clarke on 1/10/2003
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Why isn't the control not boiling off ????
Because it really isn't a 'control'. It's a separate experiment with different uncontrolled conditions. They're uncontrolled because the experimentalists don't control the right things because they all think it's 'nuclear' when it's really chemical.
Saying you've set up a 'control' is not the same as doing it. It requires knowledge of the actual control variables, not the desired or imagined ones. Reproducibility to the level of full replication on demand is required to know how to set up a true control. CF (aka LENR) has never advanced beyond the 'we get it sometimes but the level is always different' stage. That's not reproducibility.
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Another problem is that many error mechanisms are imaginary, and cannot be addressed.
Error mechanisms that can't be addressed are not real. There must be some way to test the proposal, or it is useless. This is the first thing that differentiates modern science from ancient science. You must test your hypotheses, theses, laws, whatever.
Then, assuming you can propose/devise a test, the next step is to evaluate the magnitude of the error, which you hint at with your 1/100,000 comments. That is the second most important thing modern science discovered. There is 'noise', and 'working in the noise' rarely to never leads to progress.
I also agree you can't eliminate all error mechanisms, but what you do is control and define them such that their impact is understood.
CF research really falls short on those bases.
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And some of the aforementioned cherry-picking! Brilliant.
So, pointing out that McKubre does exactly the same thing as I do, albeit with a different effect, is 'cherry picking'. Hmmmm... Then I guess pointing out all the papers where Fleischmann goes into inordinate detail on which 'k_r' to use is cherry picking too? After all F just wanted to make sure he didn't use the wrong constant and get the wrong answer, which sounds a lot like what I have said regarding the CCS.
