Mizuno's bucket of water

Quote from JedRothwell

You are saying that peer-reviewed journal papers by Fleischmann are not credible.

Yes. But I also give the reasons. A.) Inaccurate calorimetry in most cases. B.) In some cases, failure to prove the accuracy/precision of a presumed measurement method (specifically the 'video stills of foaming' method for detecting supposed 'heat-after-death' events). And I put the objections in writing for others to examine and critique. Unlike Fleischmann, who just gets irritated at his critics and throws their papers out. Hint: Fleischmann is not a god. His SERS experience should have told you that.

Quote from JedRothwell

You are telling us that a Fellow of the Royal Society writing in a peer reviewed journal is not credible.

Yes. 'Calls to authority' prove nothing JR. Garbage gets published in peer-reviewed journals all the time. Peer review just minimizes the quantity of it. Further, the CF field is well known for publishing their own stuff after 'within the group' peer review, i.e. after highly pro-biased reviewing.

Quote from JedRothwell

Who do you think you are?

I am an equivalently trained chemist with research experience is several relevant areas to the 'cold fusion' arena. Fleischmann's pedigree is not substantially different or better than mine. His publication record is better, because he went the academic route, while I went the industrial one. That usually means he would get at least 10X the publications that I do. However, that does not guarantee the correctness of said publications. Furthermore, if you'd ever read what I write, you'd understand that my view is that the whole field of CF pre-2002 was caught by an unrecognized systematic error. The failure came when they ignored my discovery and proceeded as if I was wrong.

Quote from Wyttenbach

but in kirks case the base assumptions do not agree with his logic.

That's a crazy thing to say. What can you possibly mean?

Quote from Zeus46

Just move on and stop acting so crazy.

Great advice. You should take it.

Quote from JedRothwell

Don't be ridiculous. You know damn well what I mean. I mean there were no fans or ventilation. There was plenty of cold air coming through the windows, which were single panel glass that did not shut well. As I recall, one of them was cracked. Post-war Japanese concrete buildings by that time were warped and falling to pieces. The windows would not shut.

If there was no ventilation (natural or man-made) there would have been no air flow into or out of the room, i.e. it was sealed. In a sealed room, human beings consume the O2 and exhale CO2. Eventually, CO2 levels become toxic and/or O2 levels get to low and the humans asphyxiate. That obviously didn't happen, therefore the room was not sealed, therefore there was SOME ventilation. Your 'no ventilation' is obviously wrong. Another phrase for 'ventilation' is 'air flow'. Air flow is a critical variable in calculating evaporation rates. Without air flow information, evaporation rates cannot be calculated. Which doesn't matter anyway since the experiment was never replicated.

P. S. Your 'plenty of cold air coming through the (cracked) windows' is ventilation.

Also, you don't understand Pd unloading and D2+O2 oxidation on catalysts very well either.

Quote from JedRothwell

There was plenty of cold air coming through the windows

I might also note that as the cold air coming in through the cracked windows warmed up, it would be able to hold more water vapor. Relative humidity is temperature dependent and another important variable in calculating evaporation rates.

BTW, the heaters you claim were present would also cause air flow as they added heat to the room. Hot air rises, cold air falls, nice little cycle going there.

Quote from kirkshanahan

I am an equivalently trained chemist with research experience is several relevant areas to the 'cold fusion' arena. Fleischmann's pedigree is not substantially different or better than mine. His publication record is better, because he went the academic route, while I went the industrial one. That usually means he would get at least 10X the publications that I do. However, that does not guarantee the correctness of said publications. Furthermore, if you'd ever read what I write, you'd understand that my view is that the whole field of CF pre-2002 was caught by an unrecognized systematic error. The failure came when they ignored my discovery and proceeded as if I was wrong.

I am irregular on this site but this quote I could not pass unscathed. Martin Fleischmann was one of the top 2 or 3 modern physical electrochemists - the best experimentalist I have worked with. Kirk comparing himself stretches credulity; I certainly would not compare myself to Martin. Perhaps we can cut through the chest beating and allow this group to evaluate your claims? Kirk please cite one paper where you were lead (sole or first author) that displays your skills as you would like us to see them. You claim equivalence - OK show us why. Perhaps you might also explain your "equivalent training". Martin was trained (in part) by two of the greatest men I ever knew: John Bockris and (Sir) Graham Hills at Imperial College (then the finest school of electrochemistry in the English speaking world). This was where and when modern physical electrochemistry was created (along with Frumkin in Russia). Where did you train, with whom and what did you study?

You claim that "they" (presumably including me) ignored your "discovery" and proceeded as if you were wrong. As I understand your claim, your hypothesis "explains" all FPHE results - irrespective of calorimeter specifics or method. This extravagance is the reason I largely ignore it. But OK, after you have sent and we have examined your citation (above), please explain in the simplest possible way, quantitatively, how your "unrecognized systematic error" produces error in closed cell, >99% thermal efficient, mass flow calorimetry of the sort my group performed. If error is present and unrecognized I would like to know but I have seen nothing at all in your writings that would account for such error.

I am not inviting open discussion. This thread is not useful (to me) and my discussions with you in the past have been rapidly non-convergent. Cite us your paper. Then explain your "discovery" in the context I asked. As a group we can evaluate both. I do not propose to comment further on this unless your response includes technical error in your description / analysis of SRI mass flow calorimetry; I am not encouraging this.

Quote from mmckubre

I am irregular on this site but this quote I could not pass unscathed. Martin Fleischmann was one of the top 2 or 3 modern physical electrochemists - the best experimentalist I have worked with. Kirk comparing himself stretches credulity; I certainly would not compare myself to Martin. Perhaps we can cut through the chest beating and allow this group to evaluate your claims? Kirk please cite one paper where you were lead (sole or first author) that displays your skills as you would like us to see them. You claim equivalence - OK show us why. Perhaps you might also explain your "equivalent training". Martin was trained (in part) by two of the greatest men I ever knew: John Bockris and (Sir) Graham Hills at Imperial College (then the finest school of electrochemistry in the English speaking world). This was where and when modern physical electrochemistry was created (along with Frumkin in Russia). Where did you train, with whom and what did you study?

You claim that "they" (presumably including me) ignored your "discovery" and proceeded as if you were wrong. As I understand your claim, your hypothesis "explains" all FPHE results - irrespective of calorimeter specifics or method. This extravagance is the reason I largely ignore it. But OK, after you have sent and we have examined your citation (above), please explain in the simplest possible way, quantitatively, how your "unrecognized systematic error" produces error in closed cell, >99% thermal efficient, mass flow calorimetry of the sort my group performed. If error is present and unrecognized I would like to know but I have seen nothing at all in your writings that would account for such error.

I am not inviting open discussion. This thread is not useful (to me) and my discussions with you in the past have been rapidly non-convergent. Cite us your paper. Then explain your "discovery" in the context I asked. As a group we can evaluate both. I do not propose to comment further on this unless your response includes technical error in your description / analysis of SRI mass flow calorimetry; I am not encouraging this.

Shanahan possibly (or you more likley) could quite easily put hard bounds on to what extent variation in equilibrium conditions caused by "at the electrode recombination" might affect specific results. These would be tighter than the (obvious) bound given by a limiting calorimetric efficiency of 100%. Realistically much tighter bounds could be got, given various assumptions. It would contribute to the debate for those like me who are outsiders, see an issue that might explain (part of) a collection of persistent unexpected positive excess heat results, and have found the published trail on this unsatisfactory. In the case of the SRI MFC results, with some of the tightest calorimetry around, one might expect it to be relatively easy to show results unaffected by Shanahan's suggestion, and that at least would be helpful. More helpful still would be to apply the same limiting process to other studies where one might suppose there is more possibility for significant calibration changes caused by in-cell temperature profiles changing.

Here is why I (as an outsider) find the dismissal of Shanahan's suggestions without full investigation unhelpful. If they help to explain just some part of the LENR excess heat compendium of historic results that makes any generalisations made from the others more accurate and therefore more likely to give insight into the remaining unexpected phenomenon.

Such hard limits have the merit of being grounded on known undisputed physics that all can agree.

The fact that ATER (like LENR), if it exists, is clearly an unexpected phenomena linked to very specific electrode conditions, cuts away many of the plausibility arguments used against it. That is fair, because given unexpected and unexplained observations we must examine more carefully all assumptions.

Shanahan arguments and LENR counter-arguments are summarised here (he will correct me if this is incomplete)

Storms: Reply to Shanahan's original papers

Comment on papers by K. Shanahan that propose to explain anomalous heat generated by cold fusion

https://www.sciencedirect.com/…cle/pii/S004060310500571X

Shanahan: Reply to Storms

Reply to “Comment on papers by K. Shanahan that propose to explain anomalous heat generated by cold fusion”, E. Storms, Thermochim. Acta, 2006

https://www.sciencedirect.com/…cle/pii/S0040603105005721

Marwan et al definitive reply to Shanahan:

A new look at low-energy nuclear reaction (LENR) research: a response to Shanahan. http://lenr-canr.org/acrobat/MarwanJanewlookat.pdf

Shanahan White Paper reply to Marwan et al

A Realistic Examination of Cold Fusion Claims 24 Years Later

https://drive.google.com/file/…b1doPc3otVGFUNDZKUDQ/view

The arguments on both sides have insufficient followup to determine which of the classic LENR experiments they apply to. To take one example, Marwan et al point out that 99% efficient calorimeters could be affected by CCS/ATER to at most 1% of total heat flow. True. This is exactly the type of analysis I find helpful. But they do not summarise the various excess heat experiments and state which have results clearly above such a bounding limit and therefore are provably "Shanahan-safe". From my own cursory reading I'd say very few. But a tighter bound might make safe a larger number of experiments.

Shanahan on the other hand has not attempted quantitatively to bound the effect for any significant number of experiments. While he can properly say it is not his job to do so, a decent attempt would either support or limit the scope his idea.

I see dismissal of Shanahan's views, without proper consideration, to be unhelpful. Equally Shanahan's lack of further detailed investigation means that his ideas must remain an unexpected and unproven possibility, to set against the unexpected and unproven possibility of LENR. Marwan et al dimiss Shanhan on a collection of independent plausibility arguments (which I consider improper as above) and on the proper bounding argument about calorimetric efficiency which they then do not follow through.

If those arguing that experimental results thus far prove LENR reckon this collection of excess heat experiments is not important I see no reason to conduct this analysis or be interested in Shanahan's suggestions except when designing new similar experiments. That however was not what Marwan et al argue.

If these historic experiments remain important evidence for LENR (not overweighed by other more recent results) then anyone wanting to gather more evidence about LENR as a hypothesis, and with detailed knowledge of the experiments, could properly do the bounding work.

PS - I don't see myself Shanahan as having discovered anything. Rather he has pointed out circumstances under which normal calorimetric assumptions need to be carefully re-examined when unexpected results are found (CCS) and made an unusual suggestion (ATER) for the specifics of a mechanims that might account for a collection of LENR results. Proposing a loop-hole that makes additional checking necessary is hardly a discovery, on the other hand it can be a valuable contribution to the evaluation of these results. And arguments about authority - from Shanahan or others - have no place in the analysis of experimental results other than in weighting plausibility arguments that depend on judgement. For the reason I've given above I don't think those help in this case.

Personally, I find arguments and counter-arguments over whether ATER is plausible, or whether such a novel effect could exist and not have been discovered during calibration, to be just as vacuous as the same over whether LENR is plausible, or would not have been discovered during other experiments. In fact the two explanations (ATER and LENR) are logically quite similar and both can maintain plausibility only by supposing that the effect requires unusual and not fully understood conditions. Rejecting one but not the other on plausibility arguments is unreasonable.

Shanahan, K.L.

[Please be advised I am preparing additional responses to other points from Dr. McKubre's post.]

Quote from mmckubre

Perhaps you might also explain your "equivalent training".

Before beginning that, I need to respond to the clear tone of your post, which somehow implies I am trying to besmirch the reputation of Dr. Fleischmann. I assure you I am not. However, he was a human, and thus he was capable of mistakes (as was evident from his inaccurate explanation of what became known as the Surface Enhanced Raman Effect, used in SERS), but that is not a derogatory remark since all of us make mistakes. It simply points out a fact. Systematic errors are some of the most pernicious problems that a scientist can face. What I was explicitly doing in my post that you quote is responding to Jed Rothwell's challenge to my credibility, 'my' credibility, not Fleischmann's. Since you have jumped on that bandwagon with Jed and his acolytes here, I will reply to you.

I have a Ph.D. in Physical Chemistry, thesis topic of Surface Chemistry, from the U. of California at Berkeley, granted in 1984. My research advisor was Prof. Earl Muetterties, who was an organometallic chemist of some repute, having been the Vice president or Director (i can't recall his title) of Research at E. I. DuPont de Nemours until 1973 (DuPont's Central R&D organization in Wilmington, Delaware (at least back in those days)) when he entered academia. In 1977 when he moved to Berkeley from Cornell, he established a small surface science sub-group. I joined that group in 1979. Prof. Muetterties passed away while at Berkeley, and I am likely the first of his students to graduate without his signature. My thesis was actually signed by Prof. Angelica Stacy, who still teaches there. The other members of my committee were Prof. Gabor Somorjai, a world renowned surface chemist, and Prof. Alexis Bell, a world renowned chemical engineer focused on catalysis (both still teaching at Berkeley).

While I can't substantiate my next claim for all the years concerned, I believe the following to be true, and I will gladly modify or retract the claim if I can be shown to be incorrect. The Department of Chemistry Graduate School has been among the top 10 in the world for the last 70 years or so, i.e. since roughly WWII. Many Berkeley profs participated in the Manhattan Project, and of course Glenn Seaborg worked at Berkeley for many years, along with other Nobel Prize and Priestly Award winners. When I entered in 1979, a survey had placed Berkeley at #3 in the US. This year, the US News & World Report rankings place Berkeley in a 4-way tie for #2. In 2016, Berkeley was in a 2-way tie for #1. In other words, as I stated, my pedigree to the Doctoral degree level is equivalent to Dr. Flesichmann's.

Thanks to Ahlfors for posting my publications list. It is slightly incomplete as it doesn't list technical reports, which as an industrial chemist I have many. I will not cite them all, but I will describe certain ones as they bear on my accumulated expertise in relation to the cold fusion arena.

I graduated from high school in 1973. I graduated with a B.S. honors degree from U. Nebraska-Lincoln in 1976. I had completed 1-1/2 years of undergrad research under Dr. Charles Kingsbury, having worked on two different projects. One was simply to get a FORTRAN program for 1H-NMR data from lanthanide shift reagent studies operational, which I did (after learning how to program in FORTRAN). The other was my thesis topic and involved studying the mechanism and kinetics of ketoester cyclization reactions with hydrazines via 1H-NMR, which included low temperature work.

After graduation, I worked at Sandia National Laboratory in Albuquerque, New Mexico for 3 years in two groups, the Explosive Components and Explosive Materials groups. I was initially hired as a technician, meaning I worked with a PhD staff scientist (Dr. J. Q. Searcy), however, Sandia encourages their people to perform to the limit of their abilities, and I was nearly independent after about a year. I also enrolled in the graduate chemistry department of the U. of New Mexico in Albuquerque in the Masters degree program under a Sandia continuing education program. I worked with Prof. William F. Coleman there. Initially I was going to study gas-phase luminescence of europium compounds on campus and had begun work in that arena, but after a few months my Sandia management insisted I do my thesis work at Sandia, so I had to change my topic. I chose to attempt to study a corrosion problem we had experienced via the technique of Inelastic Electron Tunneling Spectroscopy. I was to study nano-sized Ni particles deposited on alumina and treated with various chemicals of interest. Unfortunately, the lost time upset my schedule, and to complete the Masters degree I would have had to delay my entry to the Berkeley PhD program by a year, which was unacceptable. So I withdrew from UNM after 3 semesters with no degree. But this period of time familiarized me with explosives and explosives technology, thin film deposition, and liquid helium handling, and many ramifications of them that have been useful in understanding CF claims.

While at Berkeley, I procured and assembled my experimental apparatus (UHV chamber with LEED, Auger, and TDS (i.e. mass spectrometer)) , which initially led to some down time while waiting for parts to arrive. In that time period, I took up photography as a hobby, loading rolls of film, shooting photos, developing the film, and printing them. This gave me a good knowledge of film technology, which allows me to understand the issues of using dental films in supposed x-ray detection.

After graduation in 1984, and after looking for a change of pace, I joined the DuPont Dacron R&D organization with the intent of constructing a computer model of the polymerization process of high enough quality to use for direct process control (model-based process control). I spent 18 months there learning how to do what now is called 'big data' by assembling process and product historical data, and in economically justifying my project, which I found to be an issue given the poor market for Dacron at the time. So in 1986 I transferred to the TiO2 R&D group where I spent the next two years in research and quality control work. The QC work is highly relevant to the CF arena as I advanced my statistical skills to a high level and applied them to fixing broken analytical methods, which I continue to do to this day as the need arises. I also did analytical method development as part of my research, and tinkered a making nanoparticulate TiO2 (before the 'nano' prefix became a buzzword).

For personal reasons, I transferred to the Savannah River Laboratory in late 1987. DuPont left in 1989 and we have been run by various 'teams' over the years since then. We are now Savannah River National Laboratory and part of the Savannah River Site (SRS). SRS is a DOE-owned, contractor operated facility that is part of the nuclear weapons production complex. I have had multiple assignments hear as you might expect. They have included: more dynamic chemical process modeling of varying degrees of sophistication, some discrete event simulation, a touch of steady-state chemical process modeling, more SQC work, and more sensor development work, but most importantly, since 1995 I have worked with metal hydrides and all isotopes of hydrogen, include almost all of the materials claimed to show LENR, as you can see from my publications that Ahlfors has pointed out.

So, how's that for 'grandstanding'. Your turn now. Aside from your acknowledged experience in calorimetry, what do you bring to the 'LENR' table.

Fleischmann, M.

[complete list in fleish.txt]

McKubre, M.C.H.

[complete list in Mckub.txt]

Quote from kirkshanahan

I might also note that as the cold air coming in through the cracked windows warmed up, it would be able to hold more water vapor. Relative humidity is temperature dependent and another important variable in calculating evaporation rates.

Put a bucket in a room in these conditions and see if 20 L of water evaporate overnight. You will find that does not happen. You are grasping at straws here. Something like cold air entering the room will have an effect far too small to evaporate the entire bucket full of water.

You can easily test this. You should stop making assertions contrary to elementary science and common sense.

Quote from mmckubre

As I understand your claim, your hypothesis "explains" all FPHE results - irrespective of calorimeter specifics or method. This extravagance is the reason I largely ignore it. But OK, after you have sent and we have examined your citation (above), please explain in the simplest possible way, quantitatively, how your "unrecognized systematic error" produces error in closed cell, >99% thermal efficient, mass flow calorimetry of the sort my group performed.

THHuxley (THH) has pointed to several of the relevant publications. The original manuscript of my first paper in this field (sole-authorship, since you see to think 'lone-wolfery' is good) can be found on Jed Rothwell's site here: http://lenr-canr.org/acrobat/ShanahanKapossiblec.pdf The actual final version is slightly altered and is listed in Ahlfors list, but for ease:

"A Systematic Error in Mass Flow Calorimetry Demonstrated:, Kirk L. Shanahan, Thermochimica Acta, 387(2) (2002) 95-110 (Please note the word 'systematic' in the title, which is different from the manuscript's title.)

Also missing is my 2005 reply to the 2004 Szpak, Mosier-Boss, Miles, and Fleischmann publication (S. Szpak, P. A. Mosier-Boss, M. H. Miles, M. Fleischmann, Thermochimica Acta 410 (2004) 101): "Comments on 'Thermal behavior of polarized Pd/D electrodes prepared by co-deposition'" : Kirk L. Shanahan, Thermochimica Acta, 428(1-2), (2005), 207

In the simplest possible way: All CF calorimetric methods assume the temperature distribution inside the cell is unimportant. (In dynamic chemical process modeling, a subregime of chemical engineering, this is known as the 'lumped parameter' assumption.) This is only correct if it is, and must be tested to show that is so. In my first CF-related publication I test this idea. I assume (actually derive) different calibration constants for each voltage excursion used by Storms in his data used for his ICCF8 presentation by assuming there was in fact no excess heat. Then, I examine the results of that process for rationality.

I find the changes made to calibration constants to lie well-withing reported experimental variation of calibration constants. Ergo, I propose that a calibration constant shift (CCS) nullifies the exclusive claim of excess heat being present. Further I note that as this is just math, the potential problem could be present in any calibrated calorimetric experiment. (By the way, assuming one's particular calorimeter is so good it "doesn't need to be calibrated" is just assuming specific values for the calibration constants with no justification.) This leaves us collectively with an indeterminate situation. Does a CCS explain other apparent excess heat claims?

Upon examination of the extant data, I conclude it can (NOT absolutely does without a doubt). I have acknowledged many times what THH repeated, namely that there are limitations to this problem that might be exceeded, invalidating the idea that a CCS caused the observations. But no one has attempted to show such a case. Further, as THH has noted, that would also not necessarily disprove the existence of a CCS problem in other cases. Therefore, each claim of excess heat must be checked for this, but none have to date (aside from the one case where I did this for Ed Storms, much to his chagrin).

Now, to keep it simple I could stop right there. The variation in calibration constants of +/- ~3% max flat-lines a 780 mW 'excess heat' signal in a 98.4% efficient calorimeter. Roughly speaking a span of 3% means a relative standard deviation of ~1%, which based on my years of SQC experience is a top-notch technique. It would be exceptionally hard to get better than this. Yet, 780mW goes to 0 by not assuming that you can 'lump the parameters'. This is not a 'hypothesis' as you claim in your 2010 JEM publication. It is simple math.

Of course, you will ask "How can that happen?". That's natural. But it is really irrelevant. I have shown a math trick can nullify a 'big' excess heat signal ('big' because it is in a highly efficient calorimeter). The question you have to answer is "Can that happen in my work?". There is only one way to answer that question. We have to look at your math. That's why I asked twice for your calibration data, and then tried to see if anyone else knew it when you declined to answer me. Your refusal to test your data to see if a CCS might explain your results leaves us in an undetermined state: CCS or LENR?

As a conservative-minded scientist I lean towards CCS. You might be more liberal than me and lean towards LENR. But neither of us can reject the other's potential explanation without more data and analysis.

(I will address follow-on issues in a separate post to keep it simple.)

Quote from mmckubre

If error is present and unrecognized I would like to know

Doubtful. If you did you would have supplied me with your calibration equations when I twice asked for them in 1999.

Quote from mmckubre

but I have seen nothing at all in your writings that would account for such error.

That would be because of

Quote from mmckubre

I largely ignore it.

Quote from kirkshanahan

If there was no ventilation (natural or man-made) there would have been no air flow into or out of the room, i.e. it was sealed. In a sealed room, human beings consume the O2 and exhale CO2. Eventually, CO2 levels become toxic and/or O2 levels get to low and the humans asphyxiate.

I am sure you realize this is preposterous. This is a building where people worked every day, in laboratories and classrooms. Mizuno spent years there, and I spent weeks, and we are both alive. Not asphyxiated.

This has nothing to do with the discussion. Why do you say things like this? What is the point? This is trolling. You know perfectly well that any building used by people has sources of fresh air. You know what ordinary room temperature conditions are like. Conditions in a Japanese post-war concrete building in winter were different from what you are used to, but they were not so extreme as to cause 20 L to evaporate overnight. You can easily simulate these conditions. Put a bucket in a refrigerator, or leave it on the porch in winter.

You can easy test all of your hypotheses with a bucket of water. You will see that nothing you say is true, and none of it even makes sense.

Continuing with simple explanations of the CCS...

Imagine a box, with two point sources (*) of heat in it, call then P1 and P2.

|--------------------------------|

|.......................................|

|...* P1................P2 * ....|

|.......................................|

|--------------------------------|

Now assume we want to measure the power input to this box. If it makes no difference where we put the power (lumped parameter assumption) then we can do whatever we want and come up with our Pout number. (But Pout is a little less than Pin.) We then 'calibrate' by saying Pout should equal Pin, therefore we will put an 'adjusting factor', i.e. Pin = Pout, cal = k * Pout, meas (+ b in some cases).

But now, let's assume that when we put X watts into P1 we detect 99.99% of that. i.e. if no P2, k_o= k1 = 1/.9999. But for P2 we find instead that P2 = 75% of the actual P1,in. So what we get for Pout, meas = .9999*(P1,in) + .75*(P2,in). Clearly then is we fix Pin,tot to some number, how we divvy up the power between the two points will affect what Pout, meas we seem to detect. Now as long as your calibration method accounts for that, everything would be fine. But all CF calorimetrists don't do that. Instead they always apply some variant of the 'simple' calibration technique from the lumped parameter assumption.

So what they actually do is compute Pout, cal via an equation that actually looks like this

Pout, cal = k_o * (.9999*(P1,in) + .75*(P2,in)) + b (k_o is the 'overall konstant') (recall .75*P2,in = P2,out, meas)

And what is crucial to understanding the problem, all these calibrations are done in 1 of 3 ways: 1) with electrolysis using a non-active electrode (this fixes P2 to one value), 2) with a Joule heater in the high efficiency region, or 3) with a combination of 1) and 2). The key point being that P2 is either 0 in open cells, or fixed at 100% recombination in closed cells.

But now consider the case where 1W of recombination power moves from P2 to P1 (closed cell config.) Prior to the move, only 75% of that watt was detected, so the 1W would be multiplied by k_0 times .75. After the move it would be multiplied by k_0 times .9999, which is larger than what was assumed to be the case via the prior calibration. So the new Pout,cal will show an excess heat signal since Pin did not change, just its split between P1 and P2.

What this means is that because some of the power moved from P2 to P1, the calibration previously determined is no longer valid.

Moving to the 'real world' now. I believe this two-zone model approximates the real situation in part because the design of every CF cell I have ever seen has all the cell wall penetrations exiting through one limited ares (usually the 'top' of the cell). This places the primary heat loss pathways (that cause less than 100% efficiency) all in one place, and thus I believe that heat produced there is less efficiently captured by the calorimeter. However, when it moves to the electrode, it is captured more completely because it is spatially removed from the major heat loss pathways, and it is now produced in a region where liquid heat transfer dominates vs. gas heat transfer.

Open cells would have this same problem, but it would be masked even more by the fact that P2 is assumed to be 0 in all cases.

The inherent limitations to this analysis are obvious, meaning that if you get an excess heat signal that can't reasonably fit the above model, it is unlikely your apparent excess heat signal arises from this CCS/heat redistribution mechanism, as THH also has noted.

It is also obvious how one might test this. A.) Replace the electrodes with a heater that is placed in the gas space. Then simulate the above problem by calibrating with fixed but positive P2 and then lower P2 and increase P1 the same amount and see what your calibrated Pout does. Or B) redesign the cells so that not all penetrations are in the same place. (The ultimate of this would be to turn your cells upside down, which will require some modification to relocate the recombiner or vent line.)

I am done for today, see you all next week. I reserve the right to correct errors in the above posts, this was all done relatively quickly.

P.S. Jed, you still don't get it. How sad.

EDIT - L-F won't let me use spaces or tabs to get the far wall of the box to line up. Please take that into account.

2nd edit - modified the box drawing by using periods for spaces, This puts the far wall in proper alignment.

Now, to keep it simple I could stop right there. The variation in calibration constants of +/- ~3% max flat-lines a 780 mW 'excess heat' signal in a 98.4% efficient calorimeter. Roughly speaking a span of 3% means a relative standard deviation of ~1%, which based on my years of SQC experience is a top-notch technique. It would be exceptionally hard to get better than this. Yet, 780mW goes to 0 by not assuming that you can 'lump the parameters'. This is not a 'hypothesis' as you claim in your 2010 JEM publication. It is simple math.

Putting it simply, I don't see this as a physically feasible shift in mass flow calorimeters. Specifically, an efficiency of more than 100% is not possible, and temperature change in the measured cell cannot increase efficiency above 100%. Finally, the detected heat must be proportional to cell efficiency. There may be second order effects but this would seem to make positive calibration constant shift bounded +1.6%, and realistically quite a bit lower than this.

The same argument does not apply to calorimeters where close-to-cell temperatures are used as proxies for heat flow since these can have changes unrelated to calorimeter efficiency due to lack of isothermality.

I don't otherwise disagree with Kirk's point.

Quote

The same argument does not apply to calorimeters where close-to-cell temperatures are used as proxies for heat flow since these can have changes unrelated to calorimeter efficiency due to lack of isothermality

Isn't "temperature as proxy for heat flow" the principle used in all "isoperibolic" calorimeters?

Quote from seven_of_twenty

Isn't "temperature as proxy for heat flow" the principle used in all "isoperibolic" calorimeters?

Exactly. But not all of said temperatures are close to cell. Isoperibolic can be made much more independent of cell conditions with multiple isothermal wraps.

I am surprised that there is so much angst and uncertainty about this issue. This was highly discussed and heavily worked out in “the early days”. I can't speak for anyone else but I expect it is true for others as well. The phenomenon that Kirk proposes was well anticipated (and better understood) by the design team for our first mass flow calorimeter (up to 1992) and improved in both design and understanding afterwards. Our calorimeters were designed to operate on first principles (first law). Where systematic errors could conceivably occur the calorimeter was designed to be conservative - anticipated errors leading to under-measurement of heat. Some of you will remember me discussing this seemingly endlessly in 1989-1992.

We obviated the precise issue that Kirk speaks about as follows:

1. The electrochemical cell was enclosed (at pressure) in a metal heat integrator (“isothermal wrap” in THH's words).

2. Nothing left the cell except wires and a gas pipe for initial H₂or D₂gas charging.

3. A complimentary Joule heater was intimately wound into the metal heat integrator axially symmetric to the electrochemical cell.

4. The calorimetry fluid submerged and completely enveloped the integrator bathing externally all surfaces and picking up heat from wherever sourced (BTW there are 7 conspicuous heat sources in FPHE calorimeters, not just 2):

a. The anode (I * V anode)

b. The electrolyte (I² * R electrolyte)

c. The cathode (I * V cathode)

d. Any excess power

e. The recombiner (I * [V cell-V thermoneutral])

f. The complimentary Joule heater that kept the sum of input power constant (I² * R heater)

g. The wires (I² * R wire). Note that since V was measured at the calorimeter boundary only the wires inside the calorimeter contribute to this term, and it is fully measured

5. The thermal efficiency of our early design was ~98%, later improved to 99.3%.

6. Only the missing 0.7 to 2% (that is lost primarily by thermal conduction to the ambient down wires and the pipe) needs to be “calibrated”.

7. Calibration of the first law parameters (I, V, ∂m, ∂t) were performed independently of the calorimeter.

8. At constant input power the presence of excess heat can be inferred qualitatively by a rise in temperature of the outgoing fluid (normally water). Our largest excess power levels were ~300% in input power. Our largest statistical significance (Excess power / measurement uncertainty) is 90 sigma.

9. We tested our assertion that heat was measured equally independent of its source position two ways:

a. Finite element calculation (this is a complex matter not handled by two term algebra) which modeled the entire calorimeter up to its isothermal boundary: submerged in a water bath held at constant temperature ±0.003°C; in a room held constant to ±1°C

b. Experimentally testing the influence of current to the cell and the complimentary Joule heater over a wide range in blank cells (H₂O, Pt or poorly loaded Pd cathodes, early before initiation of the FPHE)

10. The calorimeters were proven to be heat-source position-independent already by 1991 when I stopped worrying about this effect for our calorimeters. The fact that long long long hours of calorimetry were performed (>100,000), covering wide variations of cell and heater power, with calorimetric registration of zero excess heat sadly but conveniently reinforces our conviction that the Shanahan hypothesis that heat excess can be incorrectly measured (always positively?) by the displacement of heat sources – plays no significant role in our calorimeters.

11. This last conclusion, equally rigorously supported by their designers and authors, applies to the two other modes of calorimetry with which I am closely familiar: F&P’s partially mirrored dewar design; the heat flow calorimetry of Violante and Energetics (using heat integrating plates).

There are more insidious potential error sources possible particularly in electrochemical calorimetry. Ed discovered one in simple isoperobolic calorimetry for which the thermal barrier was the (pyrex) cell wall (changing wall hydraulics). Others exist and we should always be alert and open to suggestion. On the other side I suggest that the suggestors pay close attention to the literature, make quantitative calculation modeling the physical processes that drive the putative mechanism, and do not make global claims of “it is all wrong because…”.

It is not that I claim that Kirk’s suggested semi-mechanism has never applied to LENR calorimetry. The effect he describes did play a role in the NRL / Coolescence Seebeck calorimeters when the recombiner is more or less well coupled to the predominant heat-flow path. But this was recognized by them. It is not that his “discovery” is never significant, or never could be. It is that the mechanism is well known, was historically anticipated, and is irrelevant to most of the calorimeters with which I am familiar. Even if he could show one case quantitatively, it would not affect the whole of our understanding.

Here endeth the lesson. I will answer only relevant technical questions for clarification (and then probably slowly).

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