Posts by kirkshanahan

    (2) I have not done the work to bound it (need to work out for myself what KS is saying about the "gamma" term). It might bound in such a way as to justify KS's statements, or not. Again this is what it would be interesting to see laid out here.


    In order to simplify your task a little I will explain. This is all in prior posts but it is scattered about and confused by the ramblings of the peanut gallery, so I’ll clarify.


    The F&P calorimetric method is actually a dynamic chemical process model heat balance equation. They construct an equation that supposedly accounts for all the instantaneous changes to the energy content of the cell. Thus they have terms for heater inputs, radiative heat loss, energy carried away with mass loss, and a term for 'excess heat'. The mass loss term is what I am discussing here. Ascoli is correct that this does not apply to the so-called ‘HAD region’, since the energy balance equation becomes undefined when the electrolyte is boiling, and since when the electrical contact is broken by electrolyte loss, the current stops.


    F&P went to great lengths to define the radiative heat loss constant ‘properly’, and this activity was the primary subject of several papers by them, including the 2004 paper by Mosier-Boss, Szpak, Miles, and Fleischmann that critcized my work, and the unpublished manuscript of Fleischmann’s that Miles published in Infinite Energy in 2017 which repeated the prior noted critcisms.


    So, to reiterate, I will discuss below the term developed to account for the energy content lost by the electrolysis gases leaving the cell. (BTW, this means this calorimetric method only applies to open cells. You wouldn’t have that term in a closed cell.)


    In the original formulation of the term, shown in Oystla’s post F&P's experiments – 30 years after CF announcement (Fig. A.3.1), there is a Greek letter ‘gamma’ at the front of this term. You have to check their glossary to see what it is, but it is a numeric measure of the ‘faradaic efficiency’, as they term it. (That is something of a misnomer if ATER (ATEC) occurs.) However, they actually apply a modified version of the original equation where they have dropped out the gamma, the one you showed in F&P's experiments – 30 years after CF announcement (also they drop a beta term too, but that’s another story.) The term is included as a loss of energy, so the leading sign is negative. Thus, by dropping the gamma, they assume it equals 1, and therefore subtract all the possible heat loss for 100% Faradaic efficiency. They then ‘tune’ their calibration constants (‘heat transfer coefficients’) to match the results of a calibration run or period of a run. They then apply that semi-empirical equation to an ‘unknown’ run.


    However, at the same time, they acknowledge that there can be up to a 2% recombination reaction occurring from a parasitic electrochemical reaction at the electrodes (this is NOT ATER/ATEC). For them, this is just 'noise' and is unimportant. This is what the so-called ‘Will’ (from Fritz Will) model models. So, they acknowledge that the faradaic efficiency can be as low as 0.98 sometimes. Therefore, if that reaction is occurring, gamma should be 0.98, not 1.0. That means their model will subtract too much heat out under those conditions (2%). The only way their model can then be matched to the real data (without changing the calibration constant) is to offset the extra loss with a gain in the term they call ‘excess heat’. In reality, that term is just an ‘error accumulator’. Having a positive value for it can arise from the impact of assumptions just as shown above, and does not force one to the conclusion that a true, extra heat source has appeared.


    Now you might think that limits the error to 2%, but you would be forgetting the Pfactor (a sub-part of the whole mass loss term). I detailed the effect in post F&P's experiments – 30 years after CF announcement . The point is that that 2% error, which F&P and SMMF consider ‘just noise’, gets increasingly magnified by the Pfactor the higher the temperature of the cell goes. As I noted 2% at 20C turns into 12% at 50C, etc.


    Now, the Will model predicts that the % electrochemical recombination will fall off as T increases, and in fact that’s what we see in the F&P data shown on the Figures (I’m recalling Fig. 6 here), so that is a confounding factor.


    But further, if the ATER or ATEC I proposed based on the Storms data occurs, that doesn’t have to follow that rule, and it will also be improperly compensated for by the ‘no-gamma’ model F&P (and later M. Miles) used. So we have two separate mechanisms that can produce less than 100% ‘Faradaic’ efficiency, yet F&P assume it is always 1.0. And most importantly, they don’t evaluate the magnitude of this error at their usual operating temperatures. The things they report as excess heat could just as easily be recombination.

    Kirk: I have not read your comment on F&P - I guess this problem (problematic assumption of thermal equilibrium in exhaust gasses) was what you identified?


    No, but you are correct that thermal equilibrium may not be obtained and that the equations' bases assume equilibrium. However, calibration doesn't require equilibrium it just requires steady state, and steady state doesn't imply equilibrium is attained either. What I have been discussing in this thread is the mathematical impact of a) the Pfactor term [ P/(P*-P) ] combined with b) the dropping of the gamma term. Those combine to make all of F&P's claims in this series of papers lie in the noise. Once that is established the rest of the arguments being made are somewhat unimportant to the final decision on the overall validity of whether F&P found 'excess heat' or not. (And just for the record, this is a separate issue from CCS/ATER (or maybe ATEC), although CCS/ATER can still apply if warranted.)

    @W


    Perhaps you should reread this: F&P's experiments – 30 years after CF announcement


    There, I show that F&P's method begins to be highly inaccurate by approx. 50C. That's why F&P said it can't be used 'near' boiling. Any discussion of using the F&P model near boiling is incorrect, because of what I outline above. Originally I missed that they admit this, but they actually do, they simply don't explain why. I do so above. In fact, all of their claims in the papers that have been discussed here so far are within the noise band, a clear sign of psuedoscience.


    Likewise, in the HAD region I long ago pointed out the temperature profile of the one claimed to show HAD was no different from the one claimed to be the 'control' . Ascoli did this also way back at the start of the prior thread on this. If one is a HAD why not the other? The whole video-basedmethod is worthless, as Pons admitted in a later paper by claiming they still needed to develop better calorimetry.


    F&P's results are all noise. Anyone who points to them as 'support' for their results being CF or LENR or LANR or CANR or... is hurting their credibility.

    haha, you have discovered something that neither Wilson, Hansen or any of the other critics found, or F&P themselves in all the discussions they had on the issue 😉


    Yes, apparently I did. It is probably because the others are 'old school' when it comes to error evaluation and don't actually evaluate it, they just wave their hands a lot, and then others accept it. Glad you appreciate it!



    P is a partial pressure and thus very small the value in P'-P will (P' ambient pressure) will never even be close to 0. It's your understanding of Chemistry that is close to 0!



    "The boiling point of a liquid varies according to the applied pressure; the normal boiling point is the temperature at which the vapour pressure is equal to the standard sea-level atmospheric pressure (760 mm [29.92 inches] of mercury). At sea level, water boils at 100° C (212° F)."


    Boiling point | chemistry | Britannica.com


    https://www.britannica.com/science/boiling-point


    -------------------




    From: http://www.wiredchemist.com/chemistry/data/vapor-pressure (Note that the last point is 758, not 658.)


    It seems it's you W who needs remedial chemistry.

    And the main point is the the F&P expressions for gas escaping the cell


    ...miss the most important fact of all, that the magnification effect of the Pfactor term covers all the reported excess heat values in the non-HAD region. Given the HAD region claims are silly too, F&P were totally working in the noise and didn't know it because they didn't quantitatively evaluate their error.

    Oystla, your calc is way off... misses the important facts...


    From Fleischmancalorimetr.pdf


    "The term [Eq. A3.2 ] is the enthalpy content of the gas stream relative to the enthalpy content at the temperature of the thermostat. The heat capacitances have been taken to be independent of the temperature and the gas stream has been assumed to be saturated with D2O vapor at the partial pressure P which applies to the cell temperature; P* is the atmospheric pressure and L is the enthalpy of evaporation of D2O which has been assumed to be independent of temperature."


    P* = 1 atm, P is the variable, P/(P*-P) will be called the Pfactor.


    For water, vapor pressure can be found here: http://www.wiredchemist.com/chemistry/data/vapor-pressure


    vp(20C) = 17.5 Torr = 0.0230 atm Pfactor = .0230/(1-.0230) = .0235

    vp(50C) = 92.5 Torr = .122 atm Pfactor = .122/(1-.122) = .139


    Pfactor ratio = 5.91


    Therefore, whatever the watts are from the electrolysis gas loss, it is counted as excess heat since F&P

    dropped the gamma term, and going from an operating temp of 20C to 50C increases that term by

    ~6X, and that gets progressively worse the higher the temp. We should be able to speak

    in percentages however, so the 'acceptable' (By F&P and Bockris) 2% error becomes a 12% error

    at 50C.


    All of the reported excess heats in the non-HAD region can be accounted for by this.


    Also note the Cp terms have a significant temperature dependence in this range. Dropping that out of the term is another error generating mechanism.

    Yes, we got him there.


    You 'got' me?


    No Alan, you don't 'got' me. First off, your experiments are not being conducted in a F&P electrolysis cell setup as I understand it, so you wouldn't expect to see at the electrode under the electrolyte recombination at all. If I'm wrong on that, I apologize. But if an F&P electrolysis cell can reliably be shown (i.e. reproducibly with control) to emit radiation, that might be a problem for an ATER mechanism. As I said to oystla, no problem. All 'proposed' chemical mechanisms are tentative anyway. Chemists learned that a long time ago. What would need to be done at that point then is to explain why a minor shift in calibration constant values can wipe out the 780 mW signal Storms obtained using 'conventional' means. ATER is simply my best guess as to what is going on. If I guessed wrong, so what?


    But what I have observed so far is that what radiation results have been reported can (1) be explained by other means, or (2) are so irreproducible and so few in number as to not be reliable anyway. As I have tried to point out many times, my objective is to get the truth, not the fantasy. If the truth is 'LENR exists'. then so be it. No skin off my nose. But that can't be proven for F&P cells as long as my criticisms are ignored or misrepresented (as per JR's favorite paper).


    Your bias is showing again.

    No. Any kind of recombination, from any source, would always result in more water left in the cell than the expected amount. The amount of water in a cell and the amount added as make-up water is measured with precision. After a day or two it would be obvious there is recombination.



    And if we could believe they accurately measured this water volume number you might be right, except for the fact that the one time it was reported in the literature, they measure 7% more volume coming out than they were supposed to get. So conservatively their measurements are in the +/- 10% range, which is not accurate enough. Further, they do not consider entrainment, which I believe ATER would alter, so that's an additional problem.


    Your position on this is based in your faith in the CFR researchers. I base my position on reported facts.


    This is enough on the invalidity of the CF field's truism on %recombination and how well it is measured from me.

    And even 100% recombination would not explain my last calculation above.


    By not working it out, you have stated something untrue.


    Recombination should be accounted for in the F&P calorimetric equation with a gamma coefficient in the P/(P*-P) term, but F&P and others drop this because they believe their own truism mentioned in prior posts. This arbitrarily sets gamma = 1, and per Will, may allow for up to a 4% error.


    The values of the P/(1-P) term (which I will call the Pterm below) for 25, 55, and 95C are respectively 0.0323, 0.1838, and 5.0317.


    In F&P's Fig. 6A, the first excess heat value they indicate is 0.303W, which occurs at a rough cell temp of 55C. If we divide the reported excess heat by the Pterm value at 55C and then multiply by the 25C value, we get 0.053W or 53mW, which could certainly be a small % electrochemical recombination. Now, do the same from 95C and we get an estimated excess heat of 8.21W, just because of the change in the Pterm.


    So to summarize, the reported excess heat could easily be a 'math trick'. It would seem to be about 50-60 mW at lower cell temps, but the Pterm effect magnifies this tremendously, for an approx. 600% error at 55C and a whopping approx. 15,500% error at 95C. Its obvious why F&P don't use their calorimetric approach at high T (close to boiling) but what they failed to realize is that the effect is big at their nominal operating temps too.


    BTW, at 500mA current, the potential recombination heat is 770mW. 10% of that is 77mW. The estimated 53mW then is about 7% (so maybe there's a little ATER going on after all). The 303 mW is still less than 100% recombination (approx. 40%).

    Well Kirk, so ATER is another ghostly phenomenon you propose, or do you have a paper proving the effect?


    Not another, the same. And in case you forgot, it has the same characteristics as LENR, so your attempt to insult my proposed mechanism equally insults LENR as a 'ghostly' phenomenon.


    I do have a paper proposing ATER as the cause of a heat distribution shift in F&P electrolysis cells, which in turn causes a calibration constant shift. ATER is a proposed mechanism, and if you can think of another one that causes heat distribution shifts, or one that explains the systematic trend noted in my paper, have at it! The more the merrier.


    I believe the attachéd graph sums it up nicely.


    If drawn in a way to make it clear, yes, I agree, and I've written it up somehwere that I can't recall at the moment. The point is the Will model for electrochemical recombination does connect several points in the Figure, and drawing said line then revels a couple of clusters of data that lie above that line, i.e., with greater excess heat than expected by the model. So I have pointed to that very graph as evidence for ATER (which derives from non-electrochemical recombination in my parlance).


    {EDIT: Storms used this graph in his 2006 attempt to rebutt my arguments, and I explained the problem in my response. Thermochimica Acta 441 (2006) 210 (Storms' paper is at p. 207.)}


    F&P ran their cells well above 0,1 A/cm2, so there would be less than 5% recombination expected.



    As I just remarked to Jed over in the 'Does LENR...' thread, your statement is based on a truism held in the CF community. That truism does not account for ATER. That's the point of my papers in the field.

    If it did, it would be readily detected after a few days because there would be more water left in the cell than expected.


    That statement has a couple of buried assumptions in it that I have pointed out many times. I believe the assumptions are incorrect. If someone could actually controllably reproduce the effect we might be able to prove that...


    The amount that does occur produces heat at below milliwatt levels. That is to say, it produces thousands of times less than the heat from electrolysis, or anomalous heat when it occurs. There is no way such low levels of heat could affect x-ray film.


    There's that truism again, "It (recomb.) can't go above 2%.". Wrong. The amount of potential recombination heat is easily calculated. It is current in amps times the thermoneutral voltage (1.54V for D, 1.43 for H as I recall). We have been looking at F&P's 1992-3 paper recently in another thread. One common current value there is 0.5A, so that means 0.77 W or 770 mW potential recombination heat. Not "thousands of times less than the heat from electrolysis", that fraction is also easily calculated as the ratio of the thermoneutral voltage to the cell voltage. In the F&P that was in the 5-10V range as I recall, giving a %recomb range of 30-60%.


    Complete recombination always happens in closed cells. Otherwise, the cells explode.


    No, not always. Check McKubre's papers, he reports recombiner failures due to getting electrolyte on them, which is why in the M series calorimeter (and perhaps others he built) he put a little cone-shaped barrier between the liquid level and the recombiner. And yes, when the recombiner stops working, the cells explode in some cases.


    It always happens above the waterline, and it never affects x-ray film. It does not affect x-ray film in the electrolyte,


    No, ATER means 'at-the-electrode-recombination', which is below the waterline, and which certainly could affect film in the vivinity.


    ... or outside the cell, and it does not affect any other type of x-ray detector. This is easily confirmed in blank runs with Pt-H and with Pd-D runs that fail to produce excess heat.


    Outside the cell is a different issue, agreed. The Cellucci paper you referenced suggests such happens. I personally doubt their explanation but I don't feel like giving you more info to trash without any thought.


    See my prior post above about 'blank' runs. Does LENR produce harmful radiations?

    Significant recombination never happens in an open cell.


    This is the truism that the CF community holds onto for dear life. It isn't necessarily true. Just think of 'anomalous excess heat' as non-electrochemical recombination, and realize that this is the very issue I bring out with my publications in this field.

    If this were a problem, why does it never happen with Pt-H and other control runs? Why does it only happen with Pd-D under certain well-defined electrochemical conditions when anomalous heat occurs? The anomalous heat cannot be the cause of it, because many cells are hotter in control runs with electrolysis heat only. (In other words, tests that do not produce excess power sometimes consume more power overall than the ones that produce excess heat plus input electrolysis power.)


    In a 'normal' F&P electrolysis-type cell, there is no ATER. I would speculate that means the measured temperature is good for all parts of the cell, which means in IR space, everything is uniform, i.e., nothing to distinguish the cathode from the electrolyte from anything else in the vicinity. When ATER starts up, this produces a localized extra heat (not excess) that is transmitted through thermal conduction in the metal mesh, making it somewhat hotter than the electrolyte. Now one can distinguish differences in IR (heat) sensitive images. What the extent and duration of the heating is would be dependent on a lot of variables.


    Note that a cell running hotter than one that shows anomalous excess heat is still thermally uniform, thus no image formation would result. It might be interesting to compare thermal fogging levels of different temp-time exposure profiles in non-AHE cells.