FP's experiments discussion

    Quote from JedRothwell

    He did not ignore that. He showed conclusively that no such droplets exist, with several methods, mainly by showing that all of the salt was left in the cell. [...]


    No doubt, you will ignore what Fleischmann wrote and you will continue to repeat that nonsense, but you should be aware that anyone who reads the literature will see that you are wrong.


    Nope! I take in great consideration what Fleischmann wrote.


    Surely F&P were aware of the droplet issue. In their paper "Calorimetry of the palladium-deuterium-heavy water system" submitted to the J. of Electroanal. Chem. on December 1989 (1), we can read: "A number of important conclusions follow from these time dependences: […] thirdly, we have found that cells are frequently driven to the boiling point, e.g. see Fig. 11. The rate of enthalpy production must become extremely large under these conditions since the dominant mode of heat transfer is now the latent heat of evaporation (see Appendix 3). It is not possible, however, at this stage to make a quantitative estimate of the heat output since the cells and instrumentation are unsuitable for making estimates under these conditions. It should also be noted that, although the cell potential initially decreases (in common to the situation for the bursts) there is usually a change to an increase of the potential with time when cells are driven to the boiling point probably due to the loss of electrolyte in spray leaving the cells." [bold added]


    Formula (A3.2) in Appendix 3 ("“Black box” models of the calorimeter") includes the enthalpy of evaporation L, but in a way which was unsuitable to take into account the heat of evaporation at boiling point, as well as the influence of the entrained droplets, as would have been mandatory in the calculation of this fundamental component of the enthalpy balance. In the gargantuan black box model of their calorimeter, they have incredibly omitted to add a couple of very simple terms into the enthalpy and mass balances for modelling this well known effect. They should have considered the possibility of "loss of electrolyte in spray leaving the cells", then demonstrated that this term was zero for each one of the tests discussed in their papers!


    The same omission is repeated in the paper presented at ICCF3 (2). Also in this case, the authors presented an enormous formula for "Modelling of the calorimeter", which didn't include the terms for the boiling phase, notwithstanding the paper was aimed to describe the high excess heat alleged to be generated at this condition.


    They then spent many pages dealing with the "Precision and Accuracy of the Heat Transfer Coefficients", in which they introduced a term "beta" to account for "a more rapid decrease than would be given by electrolysis alone (exposure of the solid components of the cell contents, D2O vapour carried off in the gas stream)". This means that they saw an anomalous loss of electrolyte during the test, but they wrongly attributed this loss entirely to D2O carried off in the gas stream as vapour.


    Finally, at the end of their report, they included an alien calculation sheet (at page 16) fallen from heaven, where a formula - different from all the others previously illustrated - was used for computing the "Enthalpy Output In Vapour". Unjustifiably, they assumed that all the 2.5 moles - lost in the last part of the boiling phase - exited the cell as vapour, in contradiction to what they wrote at the end of 1989.


    Assuming, as you said, that they really "showed conclusively that no such droplets exist", being aware of the enormous impact of this aspect on the enthalpy balance, they should have discussed the issue in the paper, describing the methods they used to ascertain that no D2O left the cell in liquid phase, and providing the relative data. On the contrary, these justifications appeared only after Morrison raised his critique to the article published on Physics Letters A with the same title of the ICCF3 paper (3), as I already pointed out in a reply to THH (4).


    Quote

    Also, if that were the cause of apparent heat, it would happen with the control tests with platinum and ordinary water. It does not.


    Where can I find the description and the results of such control tests?


    For what I found, even with a Pt cathode, the cell temperature reaches the boiling point with a rate sufficient to boil off all the electrolyte, see Fig.1 of (5).


    Quote

    There is much else that you cannot explain, such as: Why is it boiling at all, given that the input power is far lower than during the control tests?


    If you refer to the Fig.6B of (2), the input power during the alleged HAD is not known because the authors omitted to show both the voltage and the current registered during this phase. In any case, the water remaining after the boiloff was much lower than the inventory presents during the control tests.


    Quote

    There are a whole series of questions I put to THH which he has ignored. No doubt you, too, will ignore them so I will not repeat them.

    THH has new theory that droplets of pure water can condense on the cell walls and then be driven up and out of the cell by steam. …


    I did not ignored them. As already said, I intervened in that discussion (4). Anyway, THH is able to answer your questions by himself.


    My theory is much simpler: the "loss of electrolyte in spray leaving the cells" has been recognized by F&P themselves in one early report (1).


    (1) http://lenr-canr.org/acrobat/Fleischmancalorimetr.pdf

    (2) http://lenr-canr.org/acrobat/Fleischmancalorimetra.pdf

    (3) http://lenr-canr.org/acrobat/Fleischmanreplytothe.pdf

    (4) FP's experiments discussion

    (5) http://www.lenr-canr.org/acrobat/HansenWNpddcalorim.pdf

    Quote from Ascoli65

    Where can I find the description and the results of such control tests?

    In the papers referenced already.


    Quote from Ascoli65

    For what I found, even with a Pt cathode, the cell temperature reaches the boiling point with a rate sufficient to boil off all the electrolyte, see Fig.1 of (5).

    Only when you input much more power with Pt+H2O than with Pd+D2O. During the Pd boil off, electrolysis power is 37 W, anomalous heat is 145 W. The calibrations show that the cell would not boil dry in 600 s with only 37 W of input. See p. 16:


    http://lenr-canr.org/acrobat/Fleischmancalorimetra.pdf


    Actually, it does not boil dry at all with electrolysis power only, because as soon as the electrolyte falls below the cathode and anode, input power is cut off and boiling stops abruptly. Shanahan does not understand why it stops immediately, because he does not understand that the thermal mass of a Dewar cell with a small anode and cathode is much smaller than the thermal mass of a pot on an stove.


    Quote from Ascoli65

    Surely F&P were aware of the droplet issue. In their paper "Calorimetry of the palladium-deuterium-heavy water system" submitted to the J. of Electroanal. Chem. on December 1989 (1), we can read: "A number of important conclusions follow from these time dependences: […] thirdly, we have found that cells are frequently driven to the boiling point, e.g. see Fig. 11. The rate of enthalpy production must become extremely large under these conditions since the dominant mode of heat transfer is now the latent heat of evaporation (see Appendix 3). It is not possible, however, at this stage to make a quantitative estimate of the heat output since the cells and instrumentation are unsuitable for making estimates under these conditions.

    As described in subsequent papers, they re-engineered the cells and they took several steps to ensure that droplets were not entrained and did not leave the cells. They proved this by running blank cells with Pd-H2O where the heat balance was zero; by inventorying the salts left in the cell, and by various other methods. I am sure you realize this, because I have described it many times. However, you will only point to the first paper, and you will pretend the other papers do not exist.


    Why do you do this? What is the point? Are you trying to fool readers here into thinking that Fleischmann did not test for entrainment? You are not fooling anyone who bothers to read the papers.

    Ascoli65


    One thing to note about F&P's calorimetric equation is an assumption they made back in 1990 regarding it.


    {Edit: The 1990 F&P paper is here: http://www.lenr-canr.org/acrobat/Fleischmancalorimetr.pdf}


    In Martin Fleischmann, Stanley Pons, Mark W. Anderson, Lian Jun Li and Marvin Hawkins; "Calorimetry of the palladium-deuterium-heavy water system."; J. Electroanal. Chem., 1990.

    287: p. 293., in Appendix 3, Eqn A3.1 is given as:


    (Ecell(t)-Ethermoneutral,cell*gamma)*I = [ -deltaGo/2F + eta(anodic)(t) -eta(cathodic)(t) + eta(ohmic)(t) + gamma*deltaHo/2F ] I


    gamma = Current efficiency of electrolysis towards a given reaction (per "GLOSSARY OF SYMBOLS USED".


    Gamma is maintained in Eqns. A3.2-7.


    But then they write:

    "Secondly, as has been noted in the main text, the current efficiency for D2 and O2 generation is close to unity, i.e. γ = 1." (which means they are claiming no recombination) and the gamma factor disappears from then on including in all subsequent publications AFAIK (including the ones we have been discussing). This assumption seems to be hard-wired into CFers. In "Thermal behavior of polarized Pd/D electrodes prepared by co-deposition"; S. Szpak, P.A. Mosier-Boss, M.H. Miles, M. Fleischmann; Thermochimica Acta 410 (2004) 101–107, they write:


    "The frequently cited D2 + O2 recombination reaction, as being responsible for excess enthalpy generation, is not supported by experiment (recombination of evolving gases yielded volumes that were better than 1.0% of those calculated assuming 100.0% Faradaic efficiency [9], or theoretical considerations [10]).

    {references}

    [9] S. Szpak, P.A. Mosier-Boss, R.D. Boss, J.J. Smith, Fusion Technol. 33 (1998) 38.

    [10] F. Will, J. Electroanal. Chem. 426 (1997) 177."


    (Of course this is the same paper where they have 7% excess water collected, meaning I guess that CF creates water too! ;} )


    They use this to claim my 2002 paper is "difficult to understand and therefore accept". I responded in a Comment on that paper: (K.L. Shanahan / Thermochimica Acta 428(2005) 207–212): "Unfortunately, Szpak and his coauthors (in fact, most of their colleagues in the cold fusion research field) make a fundamental mistake exactly at this point. The references cited clearly deal with electrochemical oxygen reduction, a parasitic reaction whose impact is largest at low cell current. That reaction is mediated by dissolved oxygen. This author completely agrees with this point; electrochemical reduction mediated by dissolved oxygen is not significant to the apparent excess enthalpy issue. Thus SMMF’s use of the three references to eliminate recombination as the apparent excess’ source is irrelevant." (emphasis added)


    So, aside from using the 'lumped parameter' modeling approach, they arbitrarily assume that recombination is never present by deleting the one parameter from their model that might possibly have indicated what was going on if it were included and used.

    Quote from JedRothwell

    Shanahan does not understand why it stops immediately, because he does not understand that the thermal mass of a Dewar cell with a small anode and cathode is much smaller than the thermal mass of a pot on an stove.


    Actually Jed your comment is pretty nonsensical. What you are saying is that there is no heat in the cell materials that would allow the boiling to continue for even a microsecond. I can't believe that. I can believe that those people watching the video who see an apparent cessation of boiling might mistakenly think that boiling stopped because (a) they fail to realize the predominant gas producing reaction causing the bubbling they see (electrolysis) has suddenly stopped, and (b) with the current off, the direct heating of the electrolyte causing boiling is cut off, which would drastically reduce the boiling rate. But, this is all picking at nits so I won't be continuing the argument.


    edit: P.S. I described above where some excess heat would come from to continue a little boiling after the current is cut off, but you probably missed that...

    Quote from JedRothwell

    He did not ignore that. He showed conclusively that no such droplets exist, with several methods, mainly by showing that all of the salt was left in the cell. Also, if that were the cause of apparent heat, it would happen with the control tests with platinum and ordinary water. It does not.

    They and others did more than that. F&P were exquisitely aware of the calorimetric consequences of delivering unvaporized electrolyte out of the calorimeter as well as the housekeeping issue of the need to maintain electrolyte level. Some people put pH indicator in the bubble trap (very sensitive to any "gargled" alkali). He understood it. Others understood it. They checked. It didn't happen with any practical or calorimetric consequence.


    Water does leave these cells - but as vapor in the D2 + O2 gas stream. I spent thousands of hours monitoring open cells of inferior design to the F&P "boiler". At high current these need to be frequently "watered" and we used various generations of syringe and HPLC pumps do do this job. Faraday's Law needs to be adjusted up by ~5% at 30-40‡C or so, to account for the partial pressure of D2O gas in the emerging electrolysis gas stream. Kirk quotes 7% above. I very well believe this number - it depends somewhat on geometry and temperature (of course).


    But the point is - and has not been sufficiently well emphasized or recognized in this thread - that the full price of vaporization energy has already been paid inside the calorimeter. As Jed says:

    1) Martin recognized the issue of electrolyte entrainment,

    2) took steps to design against it

    3) checked to make sure that he was right.

    4) So did others - years and years ago.

    5) There is "no there there".

    Quote from kirkshanahan

    "Secondly, as has been noted in the main text, the current efficiency for D2 and O2 generation is close to unity, i.e. γ = 1." (which means they are claiming no recombination)

    They do not claim that. They prove it, by frequently measuring the amount of electrolyte in the cell.

    Quote from kirkshanahan

    Actually Jed your comment is pretty nonsensical. What you are saying is that there is no heat in the cell materials that would allow the boiling to continue for even a microsecond. I can't believe that.

    This is a slippery slope logical fallacy. Obviously I did not mean boiling stops in a microsecond. No sensible person would take what I said to mean that. I meant it stops in a few seconds, long before the water level drops down to the Kel-F plug.


    You often falsely interpret common sense observations to mean outlandish and impossible things. For example, I said there was no strong wind in Mizuno's lab, and you carried that it extremes, claiming that I meant there was no air supply and person would suffocate there.


    Who are you trying to fool, anyway? Do you actually believe I meant it would stop in a microsecond? Or are you just trying to confuse the issue and make people think I must be wrong for some reason or other?

    Quote from mmckubre

    They and others did more than that. [...]


    And so you deliberately ignore my prior post where I directly quote Fleischmann stating that in the experiment reported in 2004, they measured an excess of water that had exited the cell. So, the point is that Fleischmann considers 7% errors acceptable, but I pointed out that 3% errors can give a 780mW excess heat signal in Ed Storms' work. Bottom line, Fleischmann (and many others) are making the data tell the story they want to hear, and ignoring what it really says.

    Quote from kirkshanahan

    I know. So what?

    So, water does not exit the cell. That's what you were talking about. You wrote:


    . . . Fleischmann stating that in the experiment reported in 2004, they measured an excess of water that had exited the cell. So, the point is that Fleischmann considers 7% errors acceptable . .


    Also, this makes no sense. It is not a 7% error if they measure it. It is a known factor that happens to be 7%. It is fully accounted for. Your statement reminds me of the assertion often made by pathological skeptics that input electrolysis power is the same as noise. No, it can be measured with great precision, and accounted for, so it is not noise and not an error.

    Quote from JedRothwell

    Also, this makes no sense. It is not a 7% error if they measure it. It is a known factor that happens to be 7%. It is fully accounted for. Your statement reminds me of the assertion often made by pathological skeptics that input electrolysis power is the same as noise. No, it can be measured with great precision, and accounted for, so it is not noise and not an error.


    Once again you prove you don't read and/or can't understand...

    Quote from JedRothwell

    Only when you input much more power with Pt+H2O than with Pd+D2O. During the Pd boil off, electrolysis power is 37 W, anomalous heat is 145 W. The calibrations show that the cell would not boil dry in 600 s with only 37 W of input. See p. 16:

    Quote from kirkshanahan

    "Secondly, as has been noted in the main text, the current efficiency for D2 and O2 generation is close to unity, i.e. γ = 1." (which means they are claiming no recombination) and the gamma factor disappears from then on including in all subsequent publications AFAIK (including the ones we have been discussing). This assumption seems to be hard-wired into CFers. In "Thermal behavior of polarized Pd/D electrodes prepared by co-deposition"; S. Szpak, P.A. Mosier-Boss, M.H. Miles, M. Fleischmann; Thermochimica Acta 410 (2004) 101–107, they write:


    If the energy (excess enthalpy) is compared/derived with a null system being run with H2O, then you indeed need not to take into account recombination. Even if you are measure e.g. closed cell temperature it's a no brainer as evaporation alway will cool down the cell and recombination will reheat it by the same amount it gave for the evaporation.


    If the cell (hypothetically) looses D2O then this would reduce the COP as you measure a to low temperature.


    Heat after death (in MJ quantities) has been documented by many researchers. We see the same and it's absolutely in agreement with the ("new") halve live formula for D-D fusion.

    Quote from kirkshanahan

    And so you deliberately ignore my prior post where I directly quote Fleischmann stating that in the experiment reported in 2004, they measured an excess of water that had exited the cell. So, the point is that Fleischmann considers 7% errors acceptable, but I pointed out that 3% errors can give a 780mW excess heat signal in Ed Storms' work. Bottom line, Fleischmann (and many others) are making the data tell the story they want to hear, and ignoring what it really says.

    I don't have you on "ignore" Kirk - although with this post I might.

    I quoted from your post - using your name [7% over-Faraday]. And explained the origin of the observation [partial pressure of D2O].

    7% errors were not made by Fleischmann ... and he would not have found them acceptable.

    Your error analysis incorrect - as has been pointed out repeatedly by many and I will not go back there.

    Your statement: "Fleischmann (and many others) are making the data tell the story they want to hear, and ignoring what it really says" is unworthy and, frankly a reason to ignore you.



    All this may be true, but as an external observer when I am pointed to F&Ps papers as definitive proof of a serious anomaly not currently understood in physics I find Ascoli's critique applies to the specific papers I read. They are not serious attempts to document that an extraordinary anomaly exists, because too incomplete.


    What you are saying is; "look, they were experts, and vastly experienced in these experiments, they understood fully the issues, and did not mention them because they had already (previously) ruled out these errors".


    From my POV with an experiment breaking known physics that is just not good enough. The contrary argument would be; "if they were so experienced, and also aware of the controversial nature of their findings, and had such secure results, why did they not properly refer back to the necessary checking and state that it actually applied, explictly quoting check methodology and how it was applied to the given measurements?"


    Thus we need one paper describing one self-contained result with calibrations, controls as needed, with all checks complete, and the detailed analysis and description of each check perhaps referenced, but with a clear statement that it was done.


    Otherwise, the results are not solid. Humans are fallible. Anyone who denies their own fallibility is doubly fallible. The way we deal with this is through careful checks and replication. Arguing that these (not complete) writeups must be solid because the authors are experts is unwise.


    F&P surely had time, if their results were as clear as the papers quoted here claim, to write up an experiment set completely with all checks explicitly mentioned as being done for the given runs, and a complete analysis therefore ruling out errors? If positive results were so uncommon that this could not be done - then how can we know these occasional results were not due to break down in one of the various assumptions made and checked in some experiments but not in the experiments that give the results? Such differences happen.


    F&P surely had motivation to generate watertight experimental results. I'd be happy to find such a paper, if anyone knows of it. Instead they have a paper summarising results: Calorimetry of the Pd-D2O system: from simplicity via complications to simplicity, that is an interesting but incomplete discussion of methodology without being a complete experimental write-up. The boil-off excess power claims are so large that with complete checking for entrainment issues strong positives could be found from vaporisation enthalpy alone making all the rest of the calorimetric calibration unnecessary (I think that is true - but have not actually checked total vaporisation enthalpy - total energy supplied vs estimates of chemical energy). Yet that was not to my knowledge done.


    It is a shame that these initial poorly documented results remain in play (on this site, at least) as contributing to balance of evidence for/against LENR. You'd expect them to be subsumed completely by subsequent better experiments, such as McKubre's own, which based on the write-ups I'd judge to be much more carefully documented. I'm sure Mike is better qualified than me to comment on that.


    Shanahan here does not have convincing arguments in all cases rebutting the claims made that these experiments show real anomalies. Some of his arguments are just wrong. The problem is lack of a single experiment replicated even by the research group finding it that clearly demonstrates the FPHE. Mike's work is the closest to this, but relies on assumptions about calibration remaining correct that are not easily shown watertight. Mike's few indubitable results are outliers and as such cannot be trusted. A whole set of positive results none convincing shows evidence of something systematic but, as Shanahan correctly points out, there are possibilities for this. Arguing those possibilities cannot hold is problematic (and untrue). Arguing that they do not always hold is true but irrelevant without a very careful analysis of which results remain after they are eliminated.


    In this weighing of evidence I'd wish that those convinced of a real calorimetric anomaly here were less willing to embrace LENR as its theoretical resolution, because that throws up so much lack of theoretical coherence, and also brings strong emotions (LENR if harnessed as might be expected would solve clean energy for the world) into play. Better to be clear about anomalies first.


    THH

    McKubre quotes in “ “:


    “I don't have you on "ignore" Kirk - although with this post I might.”


    Not officially I guess within this software, but practically ever since you refused to a) help me understand your calibration methodology (in 1999), and b) read and understand what a CCS is and why it may be likely in F&P cells/calorimeters.


    “I quoted from your post - using your name [7% over-Faraday]. “


    No, you quoted Jed Rothwell, but I see you mention what I said. (“Kirk quotes 7% above.”)


    “And explained the origin of the observation [partial pressure of D2O].”


    You claim this falls within the vapor pressure loss range. Might be. Might not. You have a tendency to ‘cite’ a lot of unpublished information. I can’t be held responsible for stuff that’s not published. That’s why it should have been published. What you are effectively asking everyone to do is to ‘trust you’. That might fly for non-controversial results (and often does), but NOT for things that will change physics as we know it. In that situation ‘trust’ is never granted. It never even comes into play. The information must be published and vetted, or else it doesn’t exist (to the rest of the world). If you really knew what was going on you could publish a recipe that someone else could follow and repeat with high % success. AFAIK, and I’ve looked, no such recipe exists. (Sure, people claim they can and did that, but their claims don’t hold up to examination.) If I am wrong on this, please point me to said recipe, because if LENR exists as you claim, it personally affects me and I need to know it.



    “7% errors were not made by Fleischmann ...”


    The quoted 2004 paper was co-authored by Fleischmann. The rule is: If your name is on it, it’s yours.


    “and he would not have found them acceptable.”


    A.) The 7% is a direct calculation based on the quoted text.

    B.) He obviously found that particular error fully acceptable. He signed off on it.

    C.) I don’t know what part of the paper F was explicitly responsible for, but signing it makes it all his. (Just like your sig on the 2010 JEM paper makes all of it yours, esp. the part where you claim I documented a ‘random’ error in my 2002 pub, after I said in 4 pubs that it was either ‘systematic’ or ‘non-random’.)


    “Your error analysis [is] incorrect - as has been pointed out repeatedly by many and I will not go back there.”


    You should, because all those comments supposedly showing I am wrong are in fact wrong. That includes you long-winded repetition of irrelevant issues here:

    Mizuno's bucket of water


    "Your statement: "Fleischmann (and many others) are making the data tell the story they want to hear, and ignoring what it really says" is unworthy and, frankly a reason to ignore you."


    You already do, so you don’t need another reason.

    Quote from kirkshanahan

    Please clarify. Which ones?


    Well, it is when you get into interminable arguments with Jed about specific details and question them. I mean, your points are all theoretically valid, and Jed is often plain wrong in not picking up your points. But, sometimes you get drawn into arguing that something is maybe possible, advancing reasons that seem practically pretty dubious even to me,, and I like to be skeptical.


    I will look our for any thing more concrete and jump on it, till then withdraw my comment which was too extreme given I'm not going to trawl back and find a good example (which therefore may indeed not exist).


    PS - over the comments on F&Ps paper and ATER I as a possible error source not controlled I agree with you. Mike's comments:


    But the point is - and has not been sufficiently well emphasized or recognized in this thread - that the full price of vaporization energy has already been paid inside the calorimeter. As Jed says:

    1) Martin recognized the issue of electrolyte entrainment,

    2) took steps to design against it


    3) checked to make sure that he was right.

    4) So did others - years and years ago.

    5) There is "no there there".


    do not help except where explicit evidence exists that this whole process has been carried out correctly in the experiments showing the strong anomalies. It is not popular here to say it, but it seems very clear to me that while anomalies discovered remain incoherent with any (even semi-empirical) theory and so variable, we must look hard at all assumptions in experimental methodology because some unconsidered and occasional factor could be the cause of the anomalies. And with so many experiments, multiple types of error are likely, so observational proofs that an assumption is good cannot be carried over to different experiments.


    And the general and unquantified observation that many people find excess heat in electrolysis experiments can in fact nicely be explained by the existence of ATER (which would nearly always lead to apparent excess heat given typical cell design). So we are down to specific experiments.

    In some free time, I chose to try to spreadsheet model the Two Zone Model of a calorimeter that was proposed as a basic example of how the CCS/ATER problem could produce artificial excess heat signals. The basic two-zone model was presented in words here: Mizuno's bucket of water


    The key concept is that there is a spatial heterogeneity in heat sensitivity. This is expressed by using two different heat capture efficiencies for the two zones. One zone is the high efficiency zone (I use ~99-99.9% here). The other zone has a lower efficiency (this is one of the prime variables, I use 70-90%). I label these variables as e1 and e2 (1=high, 2=low).

    You all will please note the calorimeter type is not relevant here, only whether or not whatever it is is sensitive to this proposed heterogeneity.


    In a normal closed F&P cell, the usual (non-FPHE) condition is 100% recombination at the recombination catalyst, which is located in Zone 2. In Zone 1, we only have ohmic heating normally. The model tests what happens if some of the recombination heat from Zone 2 moves into Zone 1, which simulates the effect of the ATER process I proposed. (However, if you have a better mechanism for moving the heat, feel free to expound.)


    The total input power is given by Vin*I (i.e., voltage_in * current). A portion of that goes to electrolyze the gases, which is given by Vth*I. Vth is the so-called thermoneutral voltage. For D2 it is 1.54V IIRC. H2 is 1.43 IIRC. So the ohmic heating is (Vin-Vth)*I.


    In a normal operation, the electrodes are not active, and using the current I as the variable, one calculates the actual measured output power as the sum of the ohmic and recombination heat as modified by the heat capture efficiencies, i.e.


    Pout, meas = e1 * (Vin-Vth)* I + e2 *Vth * I (ohmic + Zone 2 100% recombination)


    Because the efficiencies are not 100%, Pout, meas will be less than Pin. But ‘calibration’ means setting Pin = k *(Pout, meas) + b for a linear calibration, which is all I examined in my calc here. K and b are the calibration constants. For simplicity here I arbitrarily set b to 0. In this case k = 1/eff, where eff is the overall heat capture efficiency. Storms’ setup gave a 98.4% value for eff. (Note that in the real world there are unit conversion factors involved in these equations as well.) So, given Vin, Vth and I we can calculate the actual measured output power and ‘calibrate’ it.


    Next, we need to simulate the movement of heat from Zone 2 to Zone 1 to see what that does numerically. To do that we must assume a % or fraction of the recombination heat that moves. This becomes one of our variable parameters. Below I will use the fractional version of it and call it recombfr.


    The key equation in this spreadsheet is the one that calculates the new output power from which is derived the apparent excess heat. It is:


    Pout,new = e1 * (Vin-Vth) * I + e1 * (recombfr) * 1.54 * I + e2 * (1-recombfr) * (Vin-1.54) * I


    Note that now a new term is added to the Zone 1 heat which is recombfr times the 100% recombination power. But note that now it is being multiplied by the higher efficiency coefficient e1, instead of by e2 as it was in the ‘normal’ case. This reduces the Zone 2 heat (as calculated in the base ‘normal’ case) by multiplying the e2*Vth*I term by (1-recombfr). It is the e1, e2 difference that creates the apparent excess power signal.


    Next, we calculate the apparent ‘calibrated’ output power by multiplying by the ‘old’ normal-case k ( Pout,cal = k * Pout,new ). Then we subtract the true Pin (=Vin*I) from the new ‘calibrated’ Pout to get the excess power signal.


    Using volts and amps gives power in Watts. Multiply that by 1000 to get milliWatts of course.


    Please recall that I have said repeatedly that the Two Zone model is expected to be inaccurate, and that a full-blown finite element analysis would actually be needed if one expects to closely match real-world data.


    The comparative test case was the E. Storms data that was originally used to identify the CCS/ATER problem. There for a power input of c. 24W, an ~780mW excess heat signal was observed from a calorimeter that had an efficiency rating of 98.4% overall, i.e. 100/k = 98.4, based on the calibration equation used.


    Tinkering with the input parameters of the model gave some interesting results. A Zone 1 efficiency (e1) of 0.999-0.995 was used. The Zone 2 efficiency (e2) was assumed to be lower and varied. As an indicator of the potential range for variation, Ed Storms had supplied data for a calibration of the same cell but for the prior calorimeter design where the heat capturing fluid tube was not placed in contact with the top of the cell. The calibration curve for that configuration implied about a 75% heat capture efficiency. Therefore that roughly marked the lower limit of Zone 2 efficiency in most test cases. Storms maximally sent 3A through the cell, so that was what was used as ‘I’. Vin was varied over a wide range.


    The fraction of the recombination heat, which would normally appear in Zone 2, that was moved to Zone 1 was varied from 0-100%.


    Some results for the 24W Pin case:


    e1 e2 recomb% Pex(mW) eff

    .999 .95 100 228.8 98.9

    .999 .9 100 466.7 98.0

    .999 .8 100 956.0 96.1

    .999 .7 100 1467.3 94.1

    .999 .8 50 478.5 96.1

    .999 .7 50 733.6 94.1

    .999 .9 50 233.4 98.0

    .995 .9 50 224.7 97.7


    Several observations can be made.

    - All the efficiencies are pretty high, but getting above 98% is tough

    - The excess heats that would be measured are all reasonably large (hundreds of mW)

    - Higher efficiencies mean lower excess heats (but still 2-3X Storms’ proposed 80 mW error)

    - Reasonably large %recombinations are required


    It seems reasonable to claim that these results illustrate how a ‘respectable’ erroneous excess heat signal could arise in a simple setup if the heat distribution mattered to overall detection efficiency. All CF calorimetry ignores this AFAIK. It is also important to note that the type of calorimeter is not specified, just the result, so there is no magic calorimeter that automatically precludes this problem. It has to be designed to exclude this, but it won’t be if the designer ignores the possibility that this can happen.


    So, in conclusion, the Two Zone Model illustrates how an apparent excess power (heat) signal can be artificially obtained if the possibility of heterogeneous heat capture efficiency is not allowed for. The magnitude of the computed excess powers is ~3-10X the reported noise levels for most CF calorimeters. Thus if something like ATER is shifting the heat around in a real non-perfect calorimeter, one can be fooled into thinking excess heat is present, especially when baseline calorimeter noise is taken to be ‘THE’ noise.


    THH has previously noted that CCS/ATER might not account for all signals, and I have agreed with him on that. This calc gives us a crude estimate of where that limit is.


    Further, note that none of the things Dr. McKubre has brought up to date impacts these conclusions.

    Quote from JedRothwell

    In the papers referenced already.


    Only when you input much more power with Pt+H2O than with Pd+D2O. During the Pd boil off, electrolysis power is 37 W, …


    The only result of a control test that I see in the papers I referenced is the transient shown in Fig.1 of (5). It refers to a blank Pt+D2O test. The current was 0.8 A and the voltage scale is limited to a maximum value of 20 V. When the voltage curve hit the upper limit of the diagram, the cell temperature was already at 97°C and was increasing very quickly. At that point the power was only 16 W, much lower than the 37 W inputed during the Pd+D2O test described by F&P in their ICCF3 paper (1).


    Quote

    … anomalous heat is 145 W. The calibrations show that the cell would not boil dry in 600 s with only 37 W of input. See p. 16:

    http://lenr-canr.org/acrobat/Fleischmancalorimetra.pdf


    Page 16 in (1)? I saw it, very carefully. Did you see it as well? Probably not with the necessary attention, otherwise you wouldn't have addressed me to a page which contains the sloppiest enthalpy balance calculation in the CF/LENR history. Even sloppier than the calculation made in the calorimetric report of the Ecat demo carried out in January 2011


    The value of 145 W for the anomalous heat is based on the implicit assumption that all the water left the cell as dry steam. This crucial assumption is the same one that was done 20 years later to pull out of the hat the alleged 12 kW of excess heat during the magic show in Bologna.


    Quote

    As described in subsequent papers, they re-engineered the cells and they took several steps to ensure that droplets were not entrained and did not leave the cells.


    I'm talking about the calorimetric results reported by F&P in December 1992 (1). The relative tests probably started in April, 1992. Can you cite a report issued before April 1992, which explains how the cells were re-engineered to avoid the spray problem mentioned in the F&P document of December 1989 (2)?


    It's reasonable that the cells have been improved in the subsequent years by F&P and by their replicators, in particular Lonchampt. However, these improvements led to a progressive vanishing of the maximum enthalpy gain (3), and this fact is a strong indication that the first cells were affected by serious problems of droplet entrainment, which were reduced but not eliminated by re-engineering.


    This also explains why a report issued in 1992 (1), at the beginning of his long activity in the CF/LENR field, is still considered the "major paper" of Fleishmann.


    Quote

    They proved this by running blank cells with Pd-H2O where the heat balance was zero; by inventorying the salts left in the cell, and by various other methods. I am sure you realize this, because I have described it many times. However, you will only point to the first paper, and you will pretend the other papers do not exist.


    I took a look to all the F&P reports I found on the web. The only one dealing with the problem of entrained droplets is the F&P reply to the Morrison's criticism on this specific point, but the answer contains only Fleishmann-says, no concrete evidence.


    I also looked for the word "droplet" in the 470 pages of the collection of Fleishmann's letters to Miles (4), mostly devoted to calorimetry. I found only two occurrences. The first is on page 138, in the aforementioned criticism raised by Morrison in 1993: "The cell resistance rises (causing higher voltage due to the constant current mode operation) due to loss of lithium salts which was caused by sputtering of electrolytic droplets up the gas outlet tube."


    The second appears at page 197 in the translation of a Japanese paper published in 1998: "In the analysis of the boiloff event, when we took into account evaporative losses, a peak value seem to indicate excess heat, but this was only caused by an overflow, [2] and the actual signal fluctuated around the zero line. […] 2. The English word “overflow” is used here. Based on the NHE claims made during ICCF conferences and in an interview published in the Nikkei, I surmise this means losses due to unboiled fluid leaving the cell in droplets of froth."


    Quote

    You are not fooling anyone who bothers to read the papers.


    I agree. It's hard to fool anyone who bothers to read and understand the papers.


    (1) http://lenr-canr.org/acrobat/Fleischmancalorimetra.pdf

    (2) http://lenr-canr.org/acrobat/Fleischmancalorimetr.pdf

    (3) FP's experiments discussion

    (4) http://lenr-canr.org/acrobat/Fleischmanlettersfroa.pdf

    (5) http://lenr-canr.org/acrobat/HansenWNpddcalorim.pdf

    Quote from kirkshanahan

    A.) The 7% isa direct calculation based on the quoted text.

    B.) Heobviously found that particular error fully acceptable. He signed off on it.

    The 7% was not an error. It was a measured quantity. The cause of it is known, and the amount is exactly what is expected at these temperatures. An error is something you fail to measure or you cannot explain.

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